Polymers based on fused diketopyrrolopyrroles

ABSTRACT

The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula (I), wherein Y is a group of formula (II); and their use as IR absorber, organic semiconductor in organic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers according to the invention can have excellent solubility in organic solvents 10 and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes.

The present invention relates to polymers comprising one or more(repeating) unit(s) of the formula (I) and their use as IR absorber,organic semiconductor in organic devices, especially in organicphotovoltaics and photodiodes, or in a device containing a diode and/oran organic field effect transistor. The polymers according to theinvention can have excellent solubility in organic solvents andexcellent film-forming properties. In addition, high efficiency ofenergy conversion, excellent field-effect mobility, good on/off currentratios and/or excellent stability can be observed, when the polymersaccording to the invention are used in organic field effect transistors,organic photovoltaics and photodiodes.

In recent years, diketopyrrolopyrroles (DPPs) have become one of theExtensively studied organic building blocks of oligomers and polymershaving promising optoelectronic properties, especially in solar cells.Reference is made to D. Chandran and Kwang-Sup Lee, MacromolecularResearch 21 (2013) 272.

US2011/0004004 relates to compounds of the formula

and their use as organic semiconductor in organic devices, like diodes,organic field effect transistors and/or a solar cells.

WO2011/144566 relates to polymers comprising one or more (repeating)unit(s) of the formula

or a polymer of formula

wherein A is a group of formula

and their use as organic semiconductor in organic devices, especially inorganic photovoltaics (solar cells) and photodiodes, or in a devicecontaining a diode and/or an organic field effect transistor.

Daniel T. Gryko et al. Organic Letters 14 (2012) 2670 disclose asynthetic approach to π-expanded diketopyrrolopyrroles. A three-stepstrategy appears to be very general and starts with the preparation ofdiketopyrrolopyrroles followed by N-alkylation with bromoacetaldehydediethyl acetal and electrophilic aromatic substitution. The finalreaction regioselectively furnishes fluorescent dyes.

WO2013/092474 (PCT/EP2012/075762), which enjoys an earlier priority datethan the present invention, but has been published after the prioritydate of the present invention, relates to compounds of formula (III):

where Ar denotes a homo- or heteroaromatic system.

PCT/EP2014/054060, which enjoys an earlier priority date than thepresent invention, but has been published after the priority date of thepresent invention, relates to novel compounds of formula

that can be used as heterocyclic dyes of unique structure andproperties. These compounds can be obtained in a three-step synthesisfrom simple substrates.

It is one object of the present invention to provide polymers, whichshow high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability, whenused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes. Another object of the invention is to providepolymers with very low band gap, which can also be used as infrared (IR)absorbers.

Said object has been solved by (conjugated) polymers, comprising one ormore (repeating) unit(s) of the formula

whereinY is a group of formula

a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1,2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3;Ar and Ar′ denote a homo- or heteroaromatic system, which may besubstituted, or unsubstituted.R¹, R^(1′), R² and R^(2′) may be the same or different and are selectedfrom hydrogen, a C₁-C₁₀₀alkyl group which can optionally be substitutedone or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—,a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₃-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group;a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group;a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group, or—COO—C₁-C₁₈alkyl group; R³⁹ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl,C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl,Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of eachother

such as, for example,

such as, for example,

whereinX is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

especially

such as, for example,

such as, for example,

andwhereinX¹ is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—,—C(R¹⁰⁸)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))_,

R³ and R^(3′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are independently of each otherhydrogen, halogen, halogenated C₁-C₂₅alkyl, especially CF₃, cyano,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₂₅alkoxy;R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one, or more oxygen, or sulphur atoms; or C₇-C₂₅arylalkyl,R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,R¹¹ and R^(11′) are independently of each other C₁-C₂₅alkyl group,especially a C₁-C₈alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy;R¹² and R^(12′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or

, wherein R¹³ is a C₁-C₁₈alkyl group, or a tri(C₁-C₈alkyl)silyl group;R¹⁰⁴ and R^(104′) are independently of each other hydrogen, C₁-C₁₈alkyl,cyano, COOR¹⁰³, C₆-C₁₀aryl, which may optionally be substituted by G, orC₂-C₈heteroaryl, which may optionally be substituted by G,R¹⁰³ and R^(103′) are independently of each other C₁-C₁₀₀alkyl,especially C₃-C₂₅alkyl, C₁-C₂₅alkyl substituted by E and/or interruptedby D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G,R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₁₈alkoxy,R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl;C₁-C₂₅alkyl; especially C₃-C₂₅alkyl, which may be interrupted by —O—, or—S—; or —COOR¹⁰³; R¹⁰³ is as defined above;R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl,C₁-C₂₅alkyl which is substituted by E and/or interrupted by D,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, orR¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹ whereinR¹¹⁰ and R¹¹¹ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, orR¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR¹¹²—,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, orhalogen,G is E, or C₁-C₁₈alkyl, andR¹¹² and R¹¹³ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R¹¹⁴ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms,R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or

, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group;R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group,especially a C₁-C₈alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy;R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen,halogen, halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which may optionally be interrupted by one ormore oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;R¹²² and R^(122′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl.

The polymers of the present invention are preferably conjugated.Polymers, comprising a repeating unit of the formula (I) are preferred.

In a preferred embodiment the present invention is directed to polymerscomprising a repeating unit of formula

wherein Y is a group of formula

a is 0 or 1, a′ is 0 or 1, b is 0, b′ is 0, c is 0 and c′ is 0; and Ar¹and Ar^(1′) are as defined above.

In said embodiment the polymer comprises preferably one or more(repeating) unit(s) of the formula

wherein Y is a group of formula

wherein a is 0, 1, 2, or 3, especially 0, or 1; a′ is 0, 1, 2, or 3,especially 0, or 1; wherein Ar¹, Ar^(1′), Ar and Ar′ and R¹, R^(1′), R²and R^(2′) are as defined in claim 1.

More preferred a is 0, a′ is 0, b is 0, b′ is 0, c is 0 and c′ is 0.

In a preferred embodiment Ar¹ and Ar^(1′) are independently of eachother a group of formula (XIa), (XIb), (XIc), (XIe), (XIf), (XIk),(XIm), (XIn), (XIq), (XIr), (XIu), (XIw), (XIx), (XIII), such as, forexample, (XIIIa) and (XIIIb); or (XIV), such as, for example, (XIVb).Preferably, Ar¹ and Ar^(1′) are independently of each other a group offormula XIa, XIb, XIe, XIf, XIr, or XIIIa. More preferably, Ar¹ andAr^(1′) are independently of each other a group of formula XIa, XIb, orXIf, most preferred a group of formula XIa.

R¹, R^(1′), R² and R^(2′) are preferably selected from hydrogen, aC₁-C₁₀₀alkyl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or can optionally beinterrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₃-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl;a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl;a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group, or—COO—C₁-C₁₈alkyl group, wherein R³⁹ is C₁-C₁₈alkyl.

Advantageously, the polymer of the present invention, or an organicsemiconductor material, layer or component, comprising the polymer ofthe present invention can be used in organic photovoltaics (solarcells), photodiodes, in an organic field effect transistor (OFET), as IRabsorber, in thin film transistors (TFT), intergrated circuits (IC),radio frequency identification (RFID) tags, devices or components,organic light emitting diodes (OLED), organic light emitting transistors(OLET), flat panel displays, backlights of displays, laser diodes,photoconductors, photodetectors, electrophotographic devices,electrophotographic recording devices, organic memory devices, sensordevices, charge injection layers, charge transport layers or interlayersin polymer light emitting diodes (PLEDs), organic plasmon emittingdiodes (OPEDs), Schottky diodes, planarising layers, antistatic films,polymer electrolyte membranes (PEM), conducting substrates, conductingpatterns, electrode materials in batteries, alignment layers,biosensors, biochips, security markings, security devices, andcomponents or devices for detecting and discriminating DNA sequences.

The term polymer comprises oligomers as well as polymers. The oligomersof this invention have a weight average molecular weight of <4,000Daltons. The polymers of this invention preferably have a weight averagemolecular weight of 4,000 Daltons or greater, especially 4,000 to2,000,000 Daltons, very especially 10,000 to 1,000,000 Daltons, morepreferably 10,000 to 100,000 Daltons and most preferred 20,000 to 60,000Daltons. Molecular weights are determined according to high-temperaturegel permeation chromatography (HT-GPC) using polystyrene standards. Thepolymers of this invention preferably have a polydispersity of 1.01 to10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5. The polymersof the present invention are preferably conjugated.

Oligomers of the present invention preferably have a weight averagemolecular weight below 4,000 Daltons.

In an embodiment of the present invention the polymer is a polymer offormula

wherein n is usually in the range of 4 to 1000, especially 4 to 200,very especially 5 to 150.

In the definition of R¹, R^(1′), R² and R^(2′) a silyl group or asiloxanyl group means —SiR¹⁶¹R¹⁶²R¹⁶³, or —O—SiR¹⁶¹R¹⁶²R¹⁶³.

R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other hydrogen,C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substitutedwith C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶,—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy,NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted1 to 3 times by C₁-C₂₅ alkyl, halogen, cyano or C₁-C₂₅alkoxy; preferablyhydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally besubstituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl,—O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —O—(SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ or phenyl; more preferablyC₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted withC₁-C₄alkyl; C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶,—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ or phenyl; most preferably C₁-C₈alkyl,C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one, or moretimes with fluorine atoms; —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶ or—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶.R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other hydrogen,C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substitutedwith C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹,—(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy,NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted1 to 3 times by C₁-C₂₅alkyl, halogen, cyano or C₁-C₂₅alkoxy; preferablyhydrogen, C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl,—O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; more preferablyC₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹,—(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; most preferably C₁-C₈alkyl,C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one or moretimes with fluorine atoms; —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹ or—(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹.R¹⁶⁹, R¹⁷⁸ and R¹⁷¹ are independently of each other hydrogen,C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substitutedwith C₁-C₄alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃,C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy,phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₅alkyl,halogen, cyano, or C₁-C₂₅alkoxy; preferably hydrogen, C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃, or phenyl; more preferablyC₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, Si(CH₃)₃, or phenyl; mostpreferably C₁-C₈alkyl, C₁-C₈haloalkyl, especially C₁-C₈alkyl which issubstituted one or more times with fluorine atoms; or —O—Si(CH₃)₃.d is an integer from 1 to 50, preferably 1 to 40, even more preferably 1to 30, still more preferably 1 to 20, more preferably 1 to 15, stillmore preferably 1 to 10 and even more preferably 1 to 5 and mostpreferably 1 to 3.R¹⁶⁷ and R¹⁶⁸ are independently of each other hydrogen, C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, C₃-C₂₅alkenyl, or phenyl; preferably C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, or phenyl; most preferably C₁-C₂₅alkyl.

In a particularly preferred embodiment R¹⁶¹, R¹⁶² and R¹⁶³ areindependently of each other C₁-C₂₅alkyl, especially C₁-C₈alkyl;C₁-C₂₅haloalkyl, especially C₁-C₈haloalkyl, such as, for example, —CF₃,—(CH₂)₂CF₃, —(CH₂)₂(CF₂)₅CF₃ and —(CH₂)₂(CF₂)₆CF₃; C₂-C₂₅alkenyl,especially C₂-C₈alkenyl; C₃-C₁₂cycloalkyl, especially C₅-C₆cycloalkyl,which might optionally be substituted with C₁-C₄alkyl; phenyl,—O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, or —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶. In case of a group—O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶ R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each otherC₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, or phenyl. In case of a group—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ R¹⁶⁴ and R¹⁶⁵ are independently of each otherC₁-C₈alkyl, R¹⁶⁶ is C₁-C₈alkyl, or phenyl and d is an integer of 2 to 5.

Examples of groups of formula —SiR¹⁶¹R¹⁶²R¹⁶³ or —O—SiR¹⁶¹R¹⁶²R¹⁶³ areshown below:

(*—indicates the bond to the carbon atom, to which the silyl group orsiloxanyl group is connected).R² and R^(2′) may be the same or different and are preferably selectedfrom hydrogen, a C₁-C₁₀₀alkyl group which can optionally be substitutedone or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or canoptionally be interrupted by —O—, —S—, —COO— or —OCO—,a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,a C₄-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl,a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, and—COO—C₁-C₁₈alkyl.

More preferably R¹, R^(1′), R² and R^(2′) are selected from hydrogen,C₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl,C₂-C₅₀haloalkenyl, allyl, C₅-C₁₂cycloalkyl, phenyl, or naphthyl whichcan optionally be substituted one or more times with C₁-C₁₂alkyl orC₁-C₁₂alkoxy, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl and—COO—C₁-C₁₈alkyl. Even more preferably R¹, R^(1′), R² and R^(2′) are aC₁-C₅₀alkyl group. Still more preferably R¹, R^(1′), R² and R^(2′) are aC₁-C₃₆alkyl group, such as, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl,2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl,n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl,undecyl, especially n-dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, 2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl,2-decyl-tetradecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl,or tetracosyl. Preferably R¹ and R^(1′) have the same meaning andindependently R² and R^(2′) have the same meaning.

More preferably if R¹ and R^(1′) are hydrogen, R² and R^(2′) aredifferent from hydrogen, or if R¹ and R^(1′) are different from hydrogenR² and R^(2′) are hydrogen.

Most preferably R² and R^(2′) are hydrogen and R¹ and R^(1′) aredifferent from hydrogen.

Advantageously, the groups R¹, R², R^(1′) and R^(2′) can be representedby formula

wherein m1=n1+2 and m1+n1≦24. Chiral side chains, such as R¹, R², R^(1′)and R^(2′) can either be homochiral, or racemic, which can influence themorphology of the compounds.

Preferably, R¹⁰³ is independently of each other C₁-C₂₅alkyl, C₁-C₂₅alkylsubstituted by halogen, C₇-C₂₅arylalkyl, or phenyl; more preferablyC₁-C₂₅alkyl.

In a preferred embodiment Ar¹ and Ar^(1′) are independently of eachother a group of formula (XIa), (XIb), (XIc), (XIe), (XIf), (XIk),(XIm), (XIn), (XIq), (XIr), (XIu), (XIw), (XIx), (XIII), such as, forexample, (XIIIa) and (XIIIb); or (XIV), such as, for example, (XIVb).Preferably, Ar¹ and Ar^(1′) are independently of each other a group offormula XIa, XIb, XIe, XIf, XIr, or XIIIa. More preferably, Ar¹ andAr^(1′) are independently of each other a group of formula XIa, XIb, orXIf, most preferred a group of formula XIa.

Preferably, R³ and R^(3′) are independently of each other hydrogen,halogen, CF₃, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; more preferably CF₃,cyano or C₁-C₂₅alkyl; most preferred hydrogen, or C₁-C₂₅alkyl.

Preferably, R¹⁰⁴ and R^(104′) are independently of each other hydrogen,cyano or a C₁-C₂₅alkyl group, more preferably hydrogen, or a C₁-C₂₅alkylgroup, most preferred hydrogen.

Preferably, R⁴, R^(4′), R⁵, R^(5′), R⁶ and R^(6′) are independently ofeach other hydrogen, halogen, CF₃, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy,more preferably hydrogen, CF₃, cyano or C₁-C₂₅alkyl; most preferredhydrogen, or C₁-C₂₅alkyl.

Preferably R⁷, R^(7′), R⁹ and R^(9′) are independently of each otherhydrogen, C₁-C₂₅alkyl, more preferably C₄-C₂₅alkyl.

Preferably, R⁸ and R^(8′) are independently of each other hydrogen,C₁-C₂₅alkyl, C₁-C₂₅alkyl, which may optionally be interrupted by one ormore oxygen or sulphur atoms; or C₇-C₂₅arylalkyl, more preferablyhydrogen, or C₁-C₂₅alkyl.

Preferably, R¹¹ and R^(11′) are independently of each other aC₁-C₂₅alkyl group, especially a C₁-C₈alkyl group, or phenyl; morepreferably a C₁-C₈alkyl group.

Preferably, R¹² and R^(12′) are independently of each other hydrogen,C₁-C₂₅alkyl, C₁-C₂₅alkoxy, or

, wherein R¹³ is a C₁-C₁₈alkyl group, or a tri(C₁-C₈alkyl)silyl group,more preferably hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkoxy.

Preferably, Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) haveindependently of each other the meaning of Ar¹.

In a preferred embodiment Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′)are independently of each other a group of formula (XIa), (XIb), (XIc),(XIe), (XIf), (XIk), (XIm), (XIn), (XIr), (XIx), (XIz), (XIIj), (XIII),such as, for example, (XIIIa), or (XIIIb); or (XIV), such as, forexample, (XIVb). Preferably, Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′)are independently of each other a group of formula XIa, XIb, XIf, XIr,XIIj, or XIIIa. More preferably, Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ andAr^(4′) are independently of each other a group of formula XIa, XIb,XIf, or XIIj, Most preferred a group of formula XIa.

Preferably, R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of eachother hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₁₈alkoxy, morepreferably C₁-C₂₅alkyl or C₁-C₁₈alkoxy, most preferred hydrogen, orC₁-C₂₅alkyl.

R¹⁰⁷ is preferably hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen or sulphur atoms; orC₇-C₂₅arylalkyl, more preferably hydrogen, or C₁-C₂₅alkyl, mostpreferred C₄-C₂₅alkyl.

Preferably, R¹⁰⁸ and R¹⁰⁹ are independently of each other H,C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted byD, C₇-C₂₅arylalkyl, C₂-C₁₈alkenyl, or C₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹together form a five or six membered ring, which optionally can besubstituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, D is—CO—, —COO—, —S— or —O—, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN orhalogen, G is E, or C₁-C₁₈alkyl. More preferably, R¹⁰⁸ and R¹⁰⁹ areindependently of each other H, C₁-C₂₅alkyl or C₇-C₂₅arylalkyl. Mostpreferred R¹⁰⁸ and R¹⁰⁹ are independently of each other H, orC₁-C₂₅alkyl.

D is preferably —CO—, —COO—, —S— or —O—, more preferably —COO—, —S— or—O—, most preferred —S— or —O—.

Preferably, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, or halogen, morepreferably C₁-C₈alkoxy, CN, or halogen, most preferred halogen,especially F.

Preferably, R¹¹² and R¹¹³ are independently of each other H;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, more preferablyH, or C₁-C₁₈alkyl; most preferred C₁-C₁₈alkyl.

In a preferred embodiment the present invention is directed to polymerscomprising one or more (repeating) unit(s) of the formula

wherein Y is a group of formula

whereinR¹, R^(1′), R² and R^(2′) may be different, but are preferably the sameare preferably selected from hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl,C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl,C₅-C₁₂cycloalkyl, phenyl and naphthyl, which can optionally besubstituted one or more times with C₁-C₁₂alkyl or C₁-C₁₂alkoxy,—CO—C₅-C₁₂cycloalkyl and —COO—C₁-C₁₈alkyl; more preferably C₁-C₅₀alkyl;most preferred C₁-C₃₈alkyl group;a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; wherein Ar¹ and Ar^(1′) are asdefined above; and R¹⁰³, R^(103′), D and E are as defined above.

Preferably a is 0, 1, or 2, a′ is 0, 1, or 2.

a and a′ may be different, but are preferably the same. a and a′ arepreferably 0 or 1, more preferably 0.

In formula

Ar and Ar′ are selected independently of each other a homo- orheteroaromatic system, which may be substituted, or unsubstituted. Thehomo- or heteroaromatic systems, Ar and Ar′, may be different, but arepreferably the same.

The homo- or heteroaromatic system (Ar and Ar′, respectively) ispreferably selected from the group consisting of benzene, furan,thiopene, pyrrole, selenophene, benzofuran, benzothiophene, indole,benzoselenophene, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene and9H-fluorene, which may optionally be substituted. Ar and Ar′ areselected independently of each other preferably from

especially

wherein the dotted lines denotes the bonds to the 6-membered ring (thedotted line

indicates the bond to the carbon atom in para-position to the nitrogenatom, the dotted line

indicates the bond to the carbon atom in meta-position to the nitrogenatom).R¹, R^(1′), R² and R^(2′) may be the same or different and are selectedfrom hydrogen or a C₁-C₃₈alkyl group, especially where in the pair R¹,R² one is a hydrogen and the other is a C₈-C₃₆alkyl group and in thepair R^(1′), R^(2′) one is a hydrogen and the other is a C₈-C₃₆alkylgroup.R^(99′″) is hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with oneor more halogen atoms and/or interrupted by one or more oxygen atoms, ortwo moieties R⁹⁹ can form a 5 or 6 membered alkyl ring.

In another preferred embodiment Ar and Ar′ are selected independently ofeach other from

such as, for example,

such as, for example,

such as, for example,

such as, for example,

such as, for example,

R⁹¹, R^(91′) and R^(91″) are independently of each other H, halogen,especially F; cyano, C₁-C₂₅alkoxy, C₁-C₂₅alkyl substituted with one ormore halogen atoms, especially F; or C₁-C₂₅alkyl,R⁹² is H, halogen, especially F; cyano, C₁-C₂₅alkoxy, or C₁-C₂₅alkyl,R⁹⁵, R⁹⁶, R⁹⁷ and R⁹⁸ are independently of each other hydrogen, halogen,especially F; cyano, C₁-C₂₅alkyl, C₁-C₂₅alkoxy, or C₁-C₂₅alkylsubstituted with one or more halogen atoms, especially F;X⁹¹ is O, S, Se, or NR⁹⁴,X⁹² is O, S, CR⁹⁹R^(99′), or NR¹³⁰, X⁹³ is O, S, or NR¹³⁰, X⁹⁴ is O, S,or NR¹³⁰,R⁹⁴ and R¹³⁰ are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, halogen, especially F;or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen or sulphur atoms and/or is optionally substituted by oneor more halogen atoms, especially F; or C₇-C₂₅arylalkyl, andR⁹⁹, R^(99′), R^(99″) and R^(99*) are independently of each otherhydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with one or morehalogen atoms and/or interrupted by one or more oxygen atoms, or twomoieties R⁹⁹ and R^(99′) or R^(99″) and R^(99*) can form a 5 or 6membered alkyl ring, which optionally can be substituted with one ormore halogen atoms and/or interrupted by one or more oxygen atoms.Preferably R⁹⁹, R^(99′), R^(99″) and R^(99*) are independently of eachother hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with one or morehalogen atoms and/or interrupted by one or more oxygen atoms. Morepreferably R⁹⁹, R^(99′), R^(99″) and R^(99*) are independently of eachother hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl interrupted by one or moreoxygen atoms. Most preferably R⁹⁹, R^(99′), R^(99″) and R^(99*) areindependently of each other C₃-C₂₅alkyl, or C₃-C₂₅alkyl interrupted byone or more oxygen atoms.

R¹²¹, R¹²², R¹²³, R¹²⁴ and R¹²⁵ are independently of each otherhydrogen, halogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, halogen; or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, which may optionallybe interrupted by one or more oxygen or sulphur atoms and/or isoptionally substituted by one or more halogen atoms, especially F; orC₇-C₂₅arylalkyl; preferably hydrogen, halogen, C₁-C₁₈alkoxy orC₁-C₂₅alkyl; most preferably hydrogen.

Preferably, X⁹¹ is O, S, or Se, more preferably X⁹¹ is O, or S, mostpreferred, X⁹¹ is S.

Preferably, X⁹², X⁹³ and X⁹⁴ are O, or S, more preferably S.

Preferably, R⁹⁴ is hydrogen, or C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms. More preferably, R⁹⁴is C₁-C₂₅alkyl.

R⁹⁵, R⁹⁶, R⁹⁷ and R⁹⁸ are preferably hydrogen, halogen, especially F;C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with one or more halogen atoms,especially F; more preferred hydrogen or C₁-C₂₅alkyl, most preferred H.

In a preferred embodiment the present invention is directed to polymerscomprising one or more (repeating) unit(s) of the formula

whereina, b, c, a′, b′, c′, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are asdefined above,Y is a group of formula

whereinR¹, R^(1′), R² and R^(2′) may be the same or different and are selectedfrom hydrogen or a C₁-C₃₈alkyl group;R⁹¹, R^(91′) and R^(91″) are independently of each other H, halogen,especially F; cyano, C₁-C₂₅alkoxy, C₁-C₂₅alkyl substituted with one ormore halogen atoms, especially F; or C₁-C₂₅alkyl,R⁹² is H, halogen, especially F; cyano, C₁-C₂₅alkoxy, or C₁-C₂₅alkyl,R⁹⁴ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, halogen, especially F; or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, whichmay optionally be interrupted by one or more oxygen or sulphur atomsand/or is optionally substituted by one or more halogen atoms,especially F; or C₇-C₂₅arylalkyl; andR^(99′″) is hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with oneor more halogen atoms and/or interrupted by one or more oxygen atoms, ortwo groups R⁹⁹ can form a 5 or 6 membered alkyl ring.

Polymers, comprising a repeating unit (I) with Y of the formula (Ya),(Yb), (Yc), (Yd), (Ye), (Yf), (Yg), (Yh), (Yi), (Yj), (Yk), (Yl), (Ym),(Yn) and (Yo) are preferred. Polymers, comprising a repeating unit (I)with Y of the formula (Ya), (Yb), (Yd), (Yf), (Yh), (Yi), (Yj), (Ym) and(Yo) are more preferred. Polymers, comprising a repeating unit (I) withY of the formula (Yb), (Yd), (Yj) and (Yo) are most preferred.

R⁹¹ is preferably H, C₁-C₂₅alkoxy, or C₁-C₂₅alkyl; more preferredhydrogen, or C₁-C₂₅alkyl, most preferred hydrogen.R^(91′) is preferably H, C₁-C₂₅alkoxy, or C₁-C₂₅alkyl; more preferredhydrogen, or C₁-C₂₅alkyl, most preferred hydrogen.R^(91″) is preferably H, C₁-C₂₅alkoxy, or C₁-C₂₅alkyl; more preferredhydrogen, or C₁-C₂₅alkyl, most preferred hydrogen.R⁹² is preferably H, C₁-C₂₅alkoxy, or C₁-C₂₅alkyl; more preferredhydrogen, or C₁-C₂₅alkyl, most preferred hydrogen.

Among repeating units of formula Ya to Yo repeating units are morepreferred, wherein R² and R^(2′) are hydrogen. R¹ and R^(1′) may bedifferent, but are preferably the same and are selected fromC₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkenyl, which may optionally beinterrupted by one or more oxygen atoms and/or is optionally substitutedby a group E^(Si) or one or more halogen atoms, especially F;C₃-C₁₀heteroaryl; C₃-C₁₀heteroaryl, which is substituted by halogen,C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen atoms and/or is optionally substitutedby a group E^(Si) or one or more halogen atoms, especially F. Morepreferred, R¹ is C₁-C₂₅alkyl, or C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen atoms and/or is optionally substitutedby a group E^(Si) or one or more fluorine atoms. Most preferred R¹ isC₁-C₂₅alkyl.

In another preferred embodiment the present invention is directed topolymers comprising one or more (repeating) unit(s) of the formula

whereina, b, c, a′, b′, c′, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are asdefined above,Y is a group of formula

whereinR¹, R^(1′), R² and R^(2′) may be the same or different and are selectedfrom hydrogen or a C₁-C₃₈alkyl group;R⁹⁹, R^(99′), R^(99″) and R^(99*) are independently of each otherhydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl interrupted by one or more oxygenatoms; preferably C₃-C₂₅alkyl, or C₃-C₂₅alkyl which is interrupted byone or more oxygen atoms;R¹²¹, R¹²², R¹²³, R¹²⁴ and R¹²⁵ are independently of each otherhydrogen, halogen, C₁-C₁₈alkoxy or C₁-C₂₅alkyl; preferably hydrogen; andR¹³⁰ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, halogen, especially F; or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, whichmay optionally be interrupted by one or more oxygen or sulphur atomsand/or is optionally substituted by one or more halogen atoms,especially F; or C₇-C₂₅arylalkyl.

In said embodiment polymers, comprising a repeating unit (I) with Y ofthe formula (Yo*), (Yp), (Yw), (Yx), (Yy), (Yz), (Yaa), (Yab), (Yac),(Yad), (Yae), (Yaf), (Yag), (Yah), (Yai), (Yaj), (Yak), (Yal), (Yam) and(Yan) are preferred. Polymers, comprising a repeating unit (I) with Y ofthe formula (Yo*), (Yw), (Yx), (Yy), (Yz), (Yac), (Yad), (Yaf), (Yag),(Yah), (Yai), (Yak), (Yal), (Yam) and (Yan) are more preferred.Polymers, comprising a repeating unit (I) with Y of the formula (Yo*),(Yw), (Yac), (Yaf), (Yag), (Yah), (Yak) and (Yam) are even morepreferred. Polymers, comprising a repeating unit (I) with Y of theformula (Yo*), (Yaf) and (Yah), especially a repeating unit (I) with Yof the formula (Yo*), are most preferred.

Among repeating units of formula Yo* to Yan repeating units are morepreferred, wherein R² and R^(2′) are hydrogen. R¹ and R^(1′) may bedifferent, but are preferably the same and are selected from hydrogen,C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkenyl, which may optionally beinterrupted by one or more oxygen atoms and/or is optionally substitutedby a group E^(Si) or one or more halogen atoms, especially F;C₃-C₁₀heteroaryl; C₃-C₁₀heteroaryl, which is substituted by halogen,C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen atoms and/or is optionally substitutedby a group E^(Si) or one or more halogen atoms, especially F. Morepreferred, R¹ is hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen atoms and/or isoptionally substituted by a group E^(Si) or one or more fluorine atoms.Most preferred R¹ is hydrogen or C₁-C₂₅alkyl. In another preferredembodiment R¹, R^(1′), R² and R^(2′) in the repeating units of formulaYo* to Yan are hydrogen.

In another embodiment the present invention is directed to polymers,comprising (repeating) unit(s) of the formula

whereinwhereinA is a repeating unit of formula (I), and-COM¹- is a repeating unit, which has the meaning of Ar¹, wherein Ar¹ isas defined above, or is a group of formula

s is 1, t is 1, u is 0, or 1, v is 0, or 1, andAr¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are independently of each other a group offormula

wherein one of X⁵ and X⁶ is N and the other is CR¹⁴, andR¹⁷ and R^(17′) are independently of each other H, or a C₁-C₂₅alkylgroup.

Preferably Ar¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are independently of each other agroup of formula

most preferably

In a preferred embodiment -COM¹- is a group of formula (XIa), (XIb),(XIc), (XIe), (XIf), (XIk), (XIm), (XIn), (XIr), (XIx), (XIz), (XIIj),(XIII), such as, for example, (XIIIa), or (XIIIb); or (XIV), such as,for example, (XIVb). Preferably -COM¹- is a group of formula XIa, XIb,XIf, XIr, XIIj, or XIIIa. More preferably, -COM¹- is a group of formulaXIa, XIb, XIf, or XIIj; most preferred XIa.

Examples of a group of formula

In a particularly preferred embodiment the repeating unit -COM¹- is agroup of formula

where R³ and R^(3′) are independently of each other hydrogen, orC₁-C₂₅alky, R¹⁰⁴ and R^(104′) preferably are independently of each otherhydrogen, cyano or a C₁-C₂₅alkyl group, and R¹⁷ and R^(17′) areindependently of each other H, or a C₁-C₂₅alkyl group, especially aC₆-C₂₅alkyl, which may optionally be interrupted by one or more oxygenatoms.

In another preferred embodiment the repeating unit -COM¹- is a group offormula

whereinR⁴ and R⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group;R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl;R¹⁰⁷ is C₁-C₂₅alkyl, andR¹⁰⁸ and R¹⁰⁹ are independently of each other a C₁-C₂₅alkyl, which maybe interrupted by one or more oxygen atoms.

In a preferred embodiment of the present invention the polymer is acopolymer, comprising repeating units of formula

especially a copolymer of formula

wherein A and COM¹ are as defined above; n is number which results in amolecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000to 1,000,000 and most preferably 10,000 to 100,000 Daltons. n is usuallyin the range of 4 to 1000, especially 4 to 200, very especially 5 to150.

In a preferred embodiment the present invention is directed to polymers,wherein A is a repeating unit of formula (Ya), (Yb), (Yc), (Yd), (Ye),(Yf), (Yg), (Yh), (Yi), (Yj), (Yk), (Yl), (Ym), (Yn), or (Yo),especially of formula (Ya), (Yb), (Yd), (Yf), (Yh), (Yi), (Yj), (Ym), or(Yo), and very especially of formula (Yb), (Yd), (Yj), or (Yo), and

is a group of formula

where R³, R^(3′), R¹⁷ and R^(17′) are independently of each otherhydrogen, or C₁-C₂₅alkyl, and R¹⁰⁴ and R^(104′) preferably areindependently of each other hydrogen, cyano or a C₁-C₂₅alkyl group.

In another preferred embodiment the present invention is directed topolymers, wherein A is a repeating unit of formula (Yo*), (Yw), (Yx),(Yy), (Yz), (Yac), (Yad), (Yaf), (Yag), (Yah), (Yai), (Yak), (Yal),(Yam), or (Yan), especially of formula (Yo*), (Yw), (Yac), (Yaf), (Yag),(Yah), (Yak), or (Yam), very especially of the formula (Yo*), (Yaf), or(Yah), and

is a group of formula

where R³, R^(3′), R¹⁷ and R^(17′) are independently of each otherhydrogen, or C₁-C₂₅alkyl, and R¹⁰⁴ and R^(104′) preferably areindependently of each other hydrogen, cyano or a C₁-C₂₅alkyl group.Among the repeating units (Yo*), (Yaf), or (Yah) (Yo*) is morepreferred.

In another preferred embodiment the present invention is directed topolymers, wherein A is a repeating unit of formula (Ya), (Yb), (Yc),(Yd), (Ye), (Yf), (Yg), (Yh), (Yi), (Yj), (Yk), (Yl), (Ym), (Yn) and(Yo), especially of formula (Ya), (Yb), (Yd), (Yf), (Yh), (Yi), (Yj),(Ym) and (Yo), and very especially of formula (Yb), (Yd), (Yj) and (Yo),and

is a group of formula

whereinR⁴ and R⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group;R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl;R¹⁰⁷ is C₁-C₂₅alkyl,R¹⁰⁸ and R¹⁰⁹ are independently of each other a C₁-C₂₅alkyl, which maybe interrupted by one or more oxygen atoms.

In another preferred embodiment the present invention is directed topolymers, wherein A is a repeating unit of formula (Yo*), (Yw), (Yx),(Yy), (Yz), (Yac), (Yad), (Yaf), (Yag), (Yah), (Yai), (Yak), (Yal),(Yam), or (Yan), especially of formula (Yo*), (Yw), (Yac), (Yaf), (Yag),(Yah), (Yak), or (Yam), very especially of the formula (Yo*), (Yaf), or(Yah), and

is a group of formula

whereinR⁴ and R⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group;R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl;R¹⁰⁷ is C₁-C₂₅alkyl,R¹⁰⁸ and R¹⁰⁹ are independently of each other a C₁-C₂₅alkyl, which maybe interrupted by one or more oxygen atoms. Among the repeating units(Yo*), (Yaf), or (Yah) (Yo*) is more preferred.

Among the polymers of formula VII′ the polymers of formula (Ia-1),(Ia-2), (Ia-3), (Ia-4), (Ia-5), (Ia-6), (Ia-7), (Ia-8), (Ia-9), (Ia-10),(Ia-11), (Ia-12), (Ia-13), (Ia-14), (Ia-15), (Ia-16), (Ia-17), (Ia-18),(Ia-19), (Ia-20), (Ia-21), (Ia-22), (Ia-23), (Ia-24), (Ia-25), (Ia-26),(Ia-27), (Ia-28), (Ia-29) and (Ia-30), as defined in claim 9, arepreferred.

n is preferably 4 to 1000, especially 4 to 200, very especially 5 to100,R¹ is preferably a C₁-C₃₈alkyl group, especially C₈-C₃₆alkyl group,R² is hydrogen;R³ and R^(3′) are preferably hydrogen, halogen, cyano, C₁-C₂₅alkyl orC₁-C₂₅alkoxy, especially hydrogen or C₁-C₂₅alkyl;R¹⁷ and R^(17′) are preferably H, or a C₁-C₂₅alkyl group;R⁹¹, R^(91′) and R^(91″) are preferably H, or C₁-C₂₅alkyl,R⁹² is H, or C₁-C₂₅alkyl, andR⁹⁹ is C₁-C₂₅alkyl, or C₁-C₂₅alkyl.

According to one embodiment of the present invention polymers of formula(Ia-1), (Ia-3), (Ia-4), (Ia-6), (Ia-7), (Ia-8), (Ia-9), (Ia-10),(Ia-11), (Ia-13), (Ia-15) and (Ia-17) are more preferred.

Examples of polymers are polymers P-1 to P-25 shown in claim 10. PolymerP-15 is less preferred than polymers P-1 to P-14 and P-16 to P-25.

The polymers of the present invention can comprise more than 2 differentrepeating units, such as, for example, repeating units A, B and D, whichare different from each other. If the polymers comprise repeating unitsof the formula

they are preferably (random) copolymers of formula

wherein x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8,y=0.8 to 0.2, and wherein x+y=1. A is a repeating unit of formula (I),D* is a repeating unit -COM¹- and B is a repeating unit -COM¹-, or arepeating unit of formula (I); with the proviso that A, B and D* aredifferent from each other. For A and -COM¹- the same preferences applyas above.

Copolymers of formula VII can be obtained, for example, by the Suzukireaction. The condensation reaction of an aromatic boronate and ahalogenide, especially a bromide, commonly referred to as the “Suzukireaction”, is tolerant of the presence of a variety of organicfunctional groups as reported by N. Miyaura and A. Suzuki in ChemicalReviews, Vol. 95, pp. 457-2483 (1995). Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(II)acetates,tri-alykl-phosphonium salts/palladium (0) derivatives andtri-alkylphosphine/palladium (0) derivatives. Especially preferredcatalysts are 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate and, tri-tert-butylphosphoniumtetrafluoroborate ((t-Bu)₃P*HBF4)/tris(dibenzylideneacetone) dipalladium(0) (Pd₂(dba)₃) and tri-tert-butylphosphine(t-Bu)₃P/tris(dibenzylideneacetone) dipalladium (0) (Pd₂(dba)₃). Thisreaction can be applied to preparing high molecular weight polymers andcopolymers.

To prepare polymers corresponding to formula VII a dihalogenide offormula X¹⁰-A-X¹⁰ is reacted with an (equimolar) amount of a diboronicacid or diboronate corresponding to formula X¹¹-COM¹-X¹¹; or adihalogenide of formula X¹⁰-COM¹-X¹⁰ is reacted with an (equimolar)amount of a diboronic acid or diboronate corresponding to formulaX¹¹-A-X¹¹, wherein X¹⁰ is halogen, especially Br, or I; and X¹¹ isindependently in each occurrence —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, under the catalytic action of Pd andtriphenylphosphine. The reaction is typically conducted at about 0° C.to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene.Other solvents such as dimethylformamide, dioxane, dimethoxyethan andtetrahydrofuran can also be used alone, or in mixtures with an aromatichydrocarbon. An aqueous base, preferably sodium carbonate orbicarbonate, potassium phosphate, potassium carbonate or bicarbonate isused as activation agent for the boronic acid, boronate and as the HBrscavenger. A polymerization reaction may take 0.2 to 100 hours. Organicbases, such as, for example, tetraalkylammonium hydroxide, and phasetransfer catalysts, such as, for example TBAB, can promote the activityof the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int.Ed. Eng. 42 (2003) 1407 and references cited therein). Other variationsof reaction conditions are given by T. I. Wallow and B. M. Novak in J.Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G.Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Control ofmolecular weight is possible by using either an excess of dibromide,diboronic acid, or diboronate, or a chain terminator.

According to the process described in WO2010/136352 the polymerisationis carried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and anorganic phosphine or phosphonium compound,b) a base,c) a solvent or a mixture of solvents, characterized in thatthe organic phosphine is a trisubstituted phosphine of formula

or phosphonium salt thereof, wherein X″ independently of Y″ represents anitrogen atom or a C—R^(2″) group and Y″ independently of X″ representsa nitrogen atom or a C—R^(9″) group, R^(1″) for each of the two R^(1″)groups independently of the other represents a radical selected from thegroup C₁-C₂₅-alkyl, C₃-C₂₀-cycloalkyl, which includes especially bothmonocyclic and also bi- and tri-cyclic cycloalkyl radicals, C₅-C₁₄-aryl,which includes especially the phenyl, naphthyl, fluorenyl radical,C₂-C₁₃-heteroaryl, wherein the number of hetero atoms, selected from thegroup N, O, S, may be from 1 to 2, wherein the two radicals R^(1″) mayalso be linked to one another,and wherein the above-mentioned radicals R^(1″) may themselves each bemono- or poly-substituted independently of one another by substituentsselected from the group hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₃-C₈-cycloalkyl, C₂-C₉-hetero-alkyl, C₅-C₁₀-aryl, C_(2′) C₉-heteroaryl,wherein the number of hetero atoms from the group N, O, S may be from 1to 4, C₁-C₂₀-alkoxy, C₁-C₁₀-haloalkyl, hydroxy, amino of the formsNH—(C₁-C₂₀-alkyl), NH—(C₅-C₁₀-aryl), N(C₁-C₂₀-alkyl)₂, N(C₁-C₂₀-alkyl)(C₅-C₁₀-aryl), N(C₅-C₁₀-aryl)₂, N(C₁-C₂₀-alkyl/C₅-C₁₀-aryl₃)₃ ₊ ,NH—CO—C₁-C₂₀-alkyl, NH—CO—C₅-C₁₀-aryl, carboxylato of the forms COOH andCOOQ (wherein Q represents either a monovalent cation or C₁-C₈-alkyl),C₁-C₆-acyloxy, sulfinato, sulfonato of the forms SO₃H and SO₃Q′ (whereinQ′ represents either a monovalent cation, C₁-C₂₀-alkyl, or C₅-C₁₀-aryl),tri-C₁-C₆-alkylsilyl, wherein two of the mentioned substituents may alsobe bridged with one another, R^(2″)-R^(9″) represent a hydrogen, alkyl,alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl,N-(alkyl)₂, O-(aryl), NH-(aryl), N-(alkyl)(aryl), O—CO-alkyl, O—CO-aryl,F, Si(alkyl)₃, CF₃, CN, CO₂H, COH, SO₃H, CONH₂, CONH(alkyl),CON(alkyl)₂, SO₂(alkyl), SO(alkyl), SO(aryl), SO₂(aryl), SO₃(alkyl),SO₃(aryl), S-alkyl, S-aryl, NH—CO (alkyl), CO₂(alkyl), CONH₂, CO(alkyl),NHCOH, NHCO₂(alkyl), CO(aryl), CO₂(aryl) radical, wherein two or moreadjacent radicals, each independently of the other (s), may also belinked to one another so that a condensed ring system is present andwherein in R^(2″) to R^(9″) alkyl represents a hydrocarbon radicalhaving from 1 to 20 carbon atoms which may in each case be linear orbranched, alkenyl represents a mono- or poly-unsaturated hydrocarbonradical having from 2 to 20 carbon atoms which may in each case belinear or branched, cycloalkyl represents a hydrocarbon having from 3 to20 carbon atoms, aryl represents a 5- to 14-membered aromatic radical,wherein from one to four carbon atoms in the aryl radical may also bereplaced by hetero atoms from the group nitrogen, oxygen and sulfur sothat a 5- to 14-membered heteroaromatic radical is present, wherein theradicals R^(2″) to R^(9″) may also carry further substituents as definedfor R^(1″).

The organic phosphines and their synthesis are described inWO2004101581.

Preferred organic phosphines are selected from trisubstituted phosphinesof formula

Cpd. R^(1″) R^(5″) R^(6″) R^(3″) R^(4″) A-1

H H H H A-2 cyclohexyl H H H H A-3 phenyl H H H H A-4 adamantyl H H H HA-5 cyclohexyl —OCH₃ H H H A-6 cyclohexyl ¹⁾ ¹⁾ H H A-7

¹⁾ ¹⁾ H H A-8 phenyl ¹⁾ ¹⁾ H H A-9 adamantyl ¹⁾ ¹⁾ H H A-10 cyclohexyl HH ²⁾ ²⁾ A-11

H H ²⁾ ²⁾ A-12 phenyl H H ²⁾ ²⁾ A-13 adamantyl H H ²⁾ ²⁾

Examples of preferred catalysts include the following compounds:

palladium(II) acetylacetonate, palladium(0) dibenzylidene-acetonecomplexes, palladium(II) propionate,Pd₂(dba)₃: [tris(dibenzylideneacetone) dipalladium(0)],Pd(dba)₂: [bis(dibenzylideneacetone) palladium(0)],Pd(PR₃)₂, wherein PR₃ is a trisubstituted phosphine of formula VI,Pd(OAc)₂: [palladium(II) acetate], palladium(II) chloride, palladium(II)bromide, lithium tetrachloropalladate(II),PdCl₂(PR₃)₂; wherein PR₃ is a trisubstituted phosphine of formula VI;palladium(0) diallyl ether complexes, palladium(II) nitrate,PdCl₂(PhCN)₂: [dichlorobis(benzonitrile) palladium(II)],PdCl₂(CH₃CN): [dichlorobis(acetonitrile) palladium(II)], andPdCl₂(COD): [dichloro(1,5-cyclooctadiene) palladium(II)].

Especially preferred are PdCl₂, Pd₂(dba)₃, Pd(dba)₂, Pd(OAc)₂, orPd(PR₃)₂. Most preferred are Pd₂(dba)₃ and Pd(OAc)₂.

The palladium catalyst is present in the reaction mixture in catalyticamounts. The term “catalytic amount” refers to an amount that is clearlybelow one equivalent of the (hetero)aromatic compound(s), preferably0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on theequivalents of the (hetero)aromatic compound(s) used.

The amount of phosphines or phosphonium salts in the reaction mixture ispreferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%,based on the equivalents of the (hetero)aromatic compound(s) used. Thepreferred ratio of Pd:phosphine is 1:4.

The base can be selected from all aqueous and nonaqueous bases and canbe inorganic, or organic. It is preferable that at least 1.5 equivalentsof said base per functional boron group is present in the reactionmixture. Suitable bases are, for example, alkali and alkaline earthmetal hydroxides, carboxylates, carbonates, fluorides and phosphatessuch as sodium and potassium hydroxide, acetate, carbonate, fluoride andphosphate or also metal alcoholates. It is also possible to use amixture of bases. The base is preferably a lithium salt, such as, forexample, lithium alkoxides (such as, for example, lithium methoxide andlithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluorideand/or phosphate.

The at present most preferred base is aqueous LiOHxH₂O (monohydrate ofLiOH) and (waterfree) LiOH.

The reaction is typically conducted at about 0° C. to 180° C.,preferably from 20 to 160° C., more preferably from 40 to 140° C. andmost preferably from 40 to 120° C. A polymerization reaction may take0.1, especially 0.2 to 100 hours.

In a preferred embodiment of the present invention the solvent is THF,the base is LiOH*H₂O and the reaction is conducted at reflux temperatureof THF (about 65° C.).

The solvent is for example selected from toluene, xylenes, anisole, THF,2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene orsolvent mixtures comprising one or more solvents like e.g. THF/tolueneand optionally water. Most preferred is THF, or THF/water.

Advantageously, the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃,(tris(dibenzylideneacetone)dipalladium(0)) and an organic phosphine A-1to A-13,

b) LiOH, or LiOHxH₂O; and

c) THF, and optionally water. If the monohydrate of LiOH is used, nowater needs to be added.

Most preferred the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃(tris(dibenzylideneacetone)dipalladium(0)) and

b) LiOHxH₂O; and

c) THF. The palladium catalyst is present in an amount of preferablyabout 0.5 mol-%, based on the equivalents of the (hetero)aromaticcompound(s) used. The amount of phosphines or phosphonium salts in thereaction mixture is preferably about 2 mol-%, based on the equivalentsof the (hetero)aromatic compound(s) used. The preferred ratio ofPd:phosphine is about 1:4.

Preferably the polymerization reaction is conducted under inertconditions in the absence of oxygen. Nitrogen and more preferably argonare used as inert gases.

The process described in WO2010/136352 is suitable for large-scaleapplications, is readily accessible and convert starting materials tothe respective polymers in high yield, with high purity and highselectivity. The process can provide polymers having weight averagemolecular weights of at least 10,000, more preferably at least 20,000,most preferably at least 30,000. The at present most preferred polymershave a weight average molecular weight of 30,000 to 80,000 Daltons.Molecular weights are determined according to high-temperature gelpermeation chromatography (HT-GPC) using polystyrene standards. Thepolymers preferably have a polydispersibility of 1.01 to 10, morepreferably 1.1 to 3.0, most preferred 1.5 to 2.5.

If desired, a monofunctional aryl halide or aryl boronate, such as, forexample,

(X² is Br, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K) may be used as a chain-terminator in such reactions,which will result in the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

The polymers of the present invention can also be synthesized by theStille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004,14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). Toprepare polymers corresponding to formula VII a dihalogenide of formulaX¹⁰-A-X¹⁰ is reacted with a compound of formula X^(11′)-COM¹-X^(11′) ora dihalogenide of formula X¹⁰-COM¹-X¹⁰ is reacted with a compound offormula X^(11′)-A-X^(11′), wherein X^(11′) is a group —SnR²⁰⁷R²⁰⁸R²⁰⁹and X¹⁰ is as defined above, in an inert solvent at a temperature inrange from 0° C. to 200° C. in the presence of a palladium-containingcatalyst, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and areH or C₁-C₆alkyl, wherein two radicals optionally form a common ring andthese radicals are optionally branched or unbranched. It must be ensuredhere that the totality of all monomers used has a highly balanced ratioof organotin functions to halogen functions. In addition, it may proveadvantageous to remove any excess reactive groups at the end of thereaction by end-capping with monofunctional reagents. In order to carryout the process, the tin compounds and the halogen compounds arepreferably introduced into one or more inert organic solvents andstirred at a temperature of from 0 to 200° C., preferably from 30 to170° C. for a period of from 1 hour to 200 hours, preferably from 5hours to 150 hours. The crude product can be purified by methods knownto the person skilled in the art and appropriate for the respectivepolymer, for example repeated re-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example,ethers, for example diethyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl etherand tert-butyl methyl ether, hydrocarbons, for example hexane,isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols,for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol,1-butanol, 2-butanol and tert-butanol, ketones, for example acetone,ethyl methyl ketone and isobutyl methyl ketone, amides, for exampledimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,nitriles, for example acetonitrile, propionitrile and butyronitrile, andmixtures thereof.

The palladium and phosphine components should be selected analogously tothe description for the Suzuki variant.

Alternatively, the polymers of the present invention can also besynthesized by the Negishi reaction using a zinc reagent A-(ZnX¹²)₂,wherein X¹² is halogen and halides, and COM¹-(X²³)₂, wherein X²³ ishalogen or triflate, or using A-(X²³)₂ and COM¹-(ZnX²³)₂. Reference is,for example, made to E. Negishi et al., Heterocycles 18 (1982) 117-22.

Alternatively, the polymers of the present invention can also besynthesized by the Hiyama reaction using a organosilicon reagentA-(SiR²¹⁰R²¹¹R²¹²)₂, wherein R²¹⁰, R²¹¹ and R²¹² are identical ordifferent and are halogen, or C₁-C₆alkyl, and COM¹-(X²³)₂, wherein X²³is halogen or triflate, or using A-(X²³)₂ and COM¹-(SiR²¹⁰R²¹¹R²¹²)₂.Reference is, for example, made to T. Hiyama et al., Pure Appl. Chem. 66(1994) 1471-1478 and T. Hiyama et al., Synlett (1991) 845-853.

Homopolymers of the type (A)_(n) can be obtained via Yamamoto couplingof dihalides X¹⁰-A-X¹⁰, where X¹⁰ is halogen, preferably bromide.Alternatively homopolymers of the type (A)_(n) can be obtained viaoxidative polymerization of units X¹⁰-A-X¹⁰, where X¹⁰ is hydrogen, e.g.with FeCl₃ as oxidizing agent.

The compounds of the formula

are intermediates in the production of the polymers of the presentinvention and are described in PCT/EP2012/075762 and EP13157961.7 (U.S.61/773,166), which are incorporated herein by reference, and Daniel T.Gryko et al. Org. Lett., 14 (2012) 2670. a, a′, b, b′, c, c′, Y, Ar¹,Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are as defined above, and X² andX^(2′) are independently of each other halogen, especially Br, or J,ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical ordifferent and are H or C₁-C₆alkyl, wherein two radicals optionally forma common ring and these radicals are optionally branched or unbranched;—SiR²¹⁰R²¹¹R²¹², wherein R²¹⁰, R²¹¹ and R²¹² are identical or differentand are halogen, or C₁-C₆alkyl; X¹² is a halogen atom, very especiallyI, or Br; —OS(O)₂CF₃, —OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independentlyof each other hydrogen, or a C₁-C₁₀alkyl group, especially—C(CH₃)₂C(CH₃)₂—, —C(CH₃)₂CH₂C(CH₃)₂—, or —CH₂C(CH₃)₂CH₂—, and Y¹³ andY¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group.The compounds of the formula (V) can be used in the production ofpolymers.

X² and X^(2′) are preferably the same.

For a, a′, b, b′, c, c′, Y, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′)the same preferences apply as described above for the repeating units offormula (I).

Compounds of formula

where R¹, R² and Ar are as defined above, can be obtained by reacting adiketopyrrolopyrrole of formula

reacted with a compound of formula

in the presence of a base, wherein X² is Cl, Br, or I; and thensubmitting the obtained N-alkylated derivative of formula

in the presence of acid to intramolecular condensation.

The alkylation reaction is preferably carried out in the presence oftetrabutylammonium hydrogen sulfate, or K₂CO₃ in dimethylformamide(DMF).

The cyclization reaction is preferably carried out in methylene chloridein the presence of trifluoromethanesulphonic acid.

Compound (5) can, for example, be prepared starting from the DPPderivative (2) as shown in the reaction scheme below:

The bromination is carried out in a suitable solvent, like chloroform,using two equivalents of N-bromo-succinimide at a temperature between−30° C. and +50° C., preferably between −10° C. and room temperature,e.g. at 0° C.

Alternatively compounds of formula

where R¹, R² and Ar are as defined above, can be obtained by reacting adiketopyrrolopyrrole of formula

with a compound of formula

in the presence of a base, wherein X² is Cl, Br, or I; and thensubmitting the obtained N-alkylated derivative of formula

in the presence of acid to intramolecular condensation. In the acetalsand ketals, oxygen can be replaced optionally by sulphur atoms.

R⁷⁰ and R⁷¹ are independently of each other a C₁-C₂₅alkyl group whichcan optionally be substituted one or more times with C₁-C₈alkyl,C₁-C₈alkoxy and/or can optionally be interrupted by —O—, —S—, —NR³⁹—.Preferably, R⁷⁰ and R⁷¹ are independently of each other a C₁-C₂₅alkylgroup, especially a C₁-C₄alkyl group. Optionally R⁷⁰ and R⁷¹ can form afive, or six membered ring.

The alkylation reaction is preferably carried out in the presence oftetrabutylammonium hydrogen sulfate, or K₂CO₃ in dimethylformamide(DMF). The cyclization reaction is preferably carried out in methylenechloride in the presence of trifluoromethanesulphonic acid.

Compounds of formula

are preferred, wherein X² is as defined above.

Compounds of formula

are also preferred, wherein X² is as defined above. For R¹, R^(1′), R²,R^(2′), R⁹¹, R^(91′), R⁹², R⁹⁹ and R¹²¹ to R¹²⁵ the same preferencesapply as described above for the repeating units of formula (I).

Examples of preferred compounds of formula V are shown below:

The following compounds of formula (IN-1) to (IN-17) are intermediatesin the production of the compounds of formula

wherein R³ is hydrogen, halogen, especially F; cyano, C₁-C₂₅alkoxy,C₁-C₂₅alkyl substituted with

one or more halogen atoms, especially F; C₁-C₂₅alkyl,

whereinR²² to R²⁵ and R²⁹ to R³³ represent independently of each other H, F,cyano, C₁-C₂₅alkoxy, C₁-C₂₅alkyl substituted with one or more halogenatoms, especially F; or C₁-C₂₅alkyl, andR²⁶ is H, F, cyano, phenyl, C₁-C₂₅alkoxy, C₁-C₂₅alkyl substituted withone or more halogen atoms, or C₁-C₂₅alkyl;R⁹⁹, R^(99′), R^(99″) and R^(99*) are independently of each otherhydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl interrupted by one or more oxygenatoms; preferably C₃-C₂₅alkyl, or C₃-C₂₅alkyl which is interrupted byone or more oxygen atoms;R¹²¹, R¹²², R¹²³, R¹²⁴ and R¹²⁵ are independently of each otherhydrogen, halogen, C₁-C₁₈alkoxy or C₁-C₂₅alkyl; preferably hydrogen; andR¹³⁰ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, halogen, especially F; or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, whichmay optionally be interrupted by one or more oxygen or sulphur atomsand/or is optionally substituted by one or more halogen atoms,especially F; or C₇-C₂₅arylalkyl. Reference is made toPCT/EP2014/054060.

In the context of the present invention, the terms halogen, C₁-C₂₅alkylC₂-C₂₅alkenyl (C₂-C₁₈alkenyl), C₂₋₂₅alkynyl (C₂₋₁₈alkynyl), aliphaticgroups, aliphatic hydrocarbon groups, alkylene, alkenylene,cycloaliphatic hydrocarbon groups, cycloalkyl, cycloalkenyl groups,C₁-C₂₅alkoxy (C₁-C₁₈alkoxy), C₁-C₁₈perfluoroalkyl, carbamoyl groups,C₆-C₂₄aryl (C₆-C₁₈aryl), C₇-C₂₅aralkyl and heteroaryl are each definedas follows—unless stated otherwise:

Halogen is fluorine, chlorine, bromine and iodine.C₁-C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, wherepossible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl.C₂-C₂₅alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branchedalkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.C₂₋₂₅ alkynyl (C₂₋₁₈ alkynyl) is straight-chain or branched andpreferably C₂₋₈ alkynyl, which may be unsubstituted or substituted, suchas, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

An aliphatic hydrocarbon group having up to 25 carbon atoms is a linearor branched alkyl, alkenyl or alkynyl (also spelled alkinyl) grouphaving up to 25 carbon atoms as exemplified above.

Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) freevalencies, e.g. trimethylene or tetramethylene.

Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one)free valencies, e.g. —CH₂—CH═CH—CH₂—.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl groupwhich may be substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups.

A cycloaliphatic-aliphatic group is an aliphatic group substituted by acycloaliphatic group, wherein the terms “cycloaliphatic” and “aliphatic”have the meanings given herein and wherein the free valency extends fromthe aliphatic moiety. Hence, a cycloaliphatic-aliphatic group is forexample a cycloalkyl-alkyl group.

A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkylgroup, e.g. cyclohexyl-methyl.

A “cycloalkenyl group” means an unsaturated alicyclic hydrocarbon groupcontaining one or more double bonds, such as cyclopentenyl,cyclopentadienyl, cyclohexenyl and the like, which may be unsubstitutedor substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups and/or condensed with phenyl groups.

For example, a cycloalkyl or cycloalkenyl group, in particular acyclohexyl group, can be condensed one or two times with phenyl whichcan be substituted one to three times with C₁-C₄-alkyl. Examples of suchcondensed cyclohexyl groups are groups of the formulae:

in particular

which can be substituted in the phenyl moieties one to three times withC₁-C₄-alkyl.

A bivalent group of the formula XII wherein R²⁸ and R²⁷ togetherrepresent alkylene or alkenylene which may be both bonded via oxygenand/or sulfur to the thienyl residue and which may both have up to 25carbon atoms, is e.g. a group of the formula

wherein A represents linear or branched alkylene having up to 25 carbonatoms, preferably ethylene or propylene which may be substituted by oneor more alkyl groups, and Y represents oxygen or sulphur. For example,the bivalent group of the formula —Y-A-O— represents —O—CH₂—CH₂—O— or—O—CH₂—CH₂—CH₂—O—.

A group of the formula XI wherein two groups R²² to R²⁶ which are in theneighborhood of each other, together represent alkylene or alkenylenehaving up to 8 carbon atoms, thereby forming a ring, is e.g. a group ofthe formula

wherein in the group of the formula XXXII R²³ and R²⁴ together represent1,4-butylene and in the group of the formula XXXIII R²³ and R²⁴ togetherrepresent 1,4-but-2-en-ylene.

C₁-C₂₅alkoxy groups (C₁-C₁₈alkoxy groups) are straight-chain or branchedalkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy,octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy andoctadecyloxy. Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy,2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy,n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferablyC₁-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthiogroup” means the same groups as the alkoxy groups, except that theoxygen atom of the ether linkage is replaced by a sulfur atom.

C₁-C₁₈perfluoroalkyl, especially C₁-C₄perfluoroalkyl, is a branched orunbranched radical such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃,—CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)_(3.)

The term “carbamoyl group” is typically a C₁₋₁₈carbamoyl radical,preferably C₁₋₈carbamoyl radical, which may be unsubstituted orsubstituted, such as, for example, carbamoyl, methylcarbamoyl,ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

A cycloalkyl group is typically C₃-C₁₂cycloalkyl, such as, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl,cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted orsubstituted. The cycloalkyl group, in particular a cyclohexyl group, canbe condensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen and cyano. Examples of suchcondensed cyclohexyl groups are:

in particular

wherein R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵ and R¹⁵⁶ are independently of eachother C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particularhydrogen.

C₆-C₂₄aryl (C₆-C₁₈aryl) is typically phenyl, indenyl, azulenyl,naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthylenyl,fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl,naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, oranthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl,9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may beunsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl,1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or9-phenanthryl, which may be unsubstituted or substituted.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl,α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl,ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl orω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, andparticularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl,β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, orω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbongroup and aromatic hydrocarbon group may be unsubstituted orsubstituted. Preferred examples are benzyl, 2-phenylethyl,3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

Heteroaryl is typically C₂-C₂₀heteroaryl, i.e. a ring with five to sevenring atoms or a condensed ring system, wherein nitrogen, oxygen orsulfur are the possible hetero atoms, and is typically an unsaturatedheterocyclic group with five to 30 atoms having at least six conjugatedπ-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl,thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl,pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl,chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl,carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl,isoxazolyl, thienothienyl, furazanyl or phenoxazinyl, which can beunsubstituted or substituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, a carbamoyl group, a nitro group or asilyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylthio,halogen, halo-C₁-C₈alkyl, or a cyano group.

C₁-C₁₈alkyl interrupted by one or more 0 is, for example,(CH₂CH₂O)₁₋₉—R^(x), where R^(x) is H or C₁-C₁₀alkyl,CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₁₈alkyl, and R^(y′)embraces the same definitions as R^(y) or is H.

If a substituent, such as, for example R³, occurs more than one time ina group, it can be different in each occurrence.

A mixture containing a polymer of the present invention results in asemi-conducting layer comprising a polymer of the present invention(typically 5% to 99.9999% by weight, especially 20 to 85% by weight) andat least another material. The other material can be, but is notrestricted to a fraction of the same polymer of the present inventionwith different molecular weight, another polymer of the presentinvention, a semi-conducting polymer, organic small molecules, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), insulator materials like the ones described for the gatedielectric (PET, PS etc.). The polymers of the present invention can beblended with small molecules described, for example, in WO2009/047104,WO2010108873 (PCT/EP2010/053655), WO09/047104, U.S. Pat. No. 6,690,029,WO2007082584, and WO2008107089:

WO2007082584:

WO2008107089:

wherein one of Y^(1′) and Y^(2′) denotes —CH═ or ═CH— and the otherdenotes —X*—, one of Y^(3′) and Y^(4′) denotes —CH═ or ═CH— and theother denotes —X*—,

X* is —O—, —S—, —Se— or NR′″—,

R* is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20C-atoms, or aryl having 2-30 C-atoms, all of which are optionallyfluorinated or perfluorinated,R′ is H, F, Cl, Br, I, CN, straight-chain or branched alkyl or alkoxyhaving 1 to 20 C-atoms and optionally being fluorinated orperfluorinated, optionally fluorinated or perfluorinated aryl having 6to 30 C-atoms, or CO₂R″, with R″ being H, optionally fluorinated alkylhaving 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30C-atoms,R′″ is H or cyclic, straight-chain or branched alkyl with 1 to 10C-atoms, y is 0, or 1, x is 0, or 1.

The polymer can contain a small molecule, or a mixture of two, or moresmall molecule compounds.

Accordingly, the present invention also relates to an organicsemiconductor material, layer or component, comprising a polymeraccording to the present invention.

The polymers of the invention can be used as the semiconductor layer insemiconductor devices. Accordingly, the present invention also relatesto semiconductor devices, comprising a polymer of the present invention,or an organic semiconductor material, layer or component. Thesemiconductor device is especially an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor.

The polymers of the invention can be used alone or in combination as theorganic semiconductor layer of the semiconductor device. The layer canbe provided by any useful means, such as, for example, vapor deposition(for materials with relatively low molecular weight) and printingtechniques. The compounds of the invention may be sufficiently solublein organic solvents and can be solution deposited and patterned (forexample, by spin coating, dip coating, slot die coating, ink jetprinting, gravure printing, flexo printing, offset printing, screenprinting, microcontact (wave)-printing, drop or zone casting, or otherknown techniques).

The polymers of the invention can be used in integrated circuitscomprising a plurality of OTFTs, as well as in various electronicarticles. Such articles include, for example, radio-frequencyidentification (RFID) tags, backplanes for flexible displays (for usein, for example, personal computers, cell phones, or handheld devices),smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-,mechanical- or temperature sensors), especially photodiodes, or securitydevices and the like.

A further aspect of the present invention is an organic semiconductormaterial, layer or component comprising one or more polymers, orcompounds of the present invention. A further aspect is the use of thepolymers or materials of the present invention in an organicphotovoltaic (PV) device (solar cell), a photodiode, or an organic fieldeffect transistor (OFET). A further aspect is an organic photovoltaic(PV) device (solar cell), a photodiode, or an organic field effecttransistor (OFET) comprising a polymer or material of the presentinvention.

The polymers of the present invention are typically used as organicsemiconductors in form of thin organic layers or films, preferably lessthan 30 microns thick. Typically the semiconducting layer of the presentinvention is at most 1 micron (=1 μm) thick, although it may be thickerif required. For various electronic device applications, the thicknessmay also be less than about 1 micron thick. For example, for use in anOFET the layer thickness may typically be 100 nm or less. The exactthickness of the layer will depend, for example, upon the requirementsof the electronic device in which the layer is used.

For example, the active semiconductor channel between the drain andsource in an OFET may comprise a layer of the present invention.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,    -   a drain electrode,    -   a gate electrode,    -   a semiconducting layer,    -   one or more gate insulator layers, and    -   optionally a substrate, wherein the semiconductor layer        comprises one or more polymers of the present invention.

The gate, source and drain electrodes and the insulating andsemiconducting layer in the OFET device may be arranged in any sequence,provided that the source and drain electrode are separated from the gateelectrode by the insulating layer, the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and asecond side, a gate electrode located on the first side of theinsulator, a layer comprising a polymer of the present invention locatedon the second side of the insulator, and a drain electrode and a sourceelectrode located on the polymer layer.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and manufacturing methods of an OFET device areknown to the person skilled in the art and are described in theliterature, for example in WO03/052841.

The gate insulator layer may comprise for example a fluoropolymer, likee.g. the commercially available Cytop 809M®, or Cytop 107M® (from AsahiGlass). Preferably the gate insulator layer is deposited, e.g. byspin-coating, doctor blading, wire bar coating, spray or dip coating orother known methods, from a formulation comprising an insulator materialand one or more solvents with one or more fluoro atoms (fluorosolvents),preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC75®(available from Acros, catalogue number 12380). Other suitablefluoropolymers and fluorosolvents are known in prior art, like forexample the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), orFluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No.12377).

The semiconducting layer comprising a polymer of the present inventionmay additionally comprise at least another material. The other materialcan be, but is not restricted to another polymer of the presentinvention, a semi-conducting polymer, a polymeric binder, organic smallmolecules different from a polymer of the present invention, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), and insulator materials like the ones described for thegate dielectric (PET, PS etc.). As stated above, the semiconductivelayer can also be composed of a mixture of one or more polymers of thepresent invention and a polymeric binder. The ratio of the polymers ofthe present invention to the polymeric binder can vary from 5 to 95percent. Preferably, the polymeric binder is a semicristalline polymersuch as polystyrene (PS), high-density polyethylene (HDPE),polypropylene (PP) and polymethylmethacrylate (PMMA). With thistechnique, a degradation of the electrical performance can be avoided(cf. W02008/001123A1).

The polymers of the present invention are advantageously used in organicphotovoltaic (PV) devices (solar cells). Accordingly, the inventionprovides PV devices comprising a polymer according to the presentinvention. A device of this construction will also have rectifyingproperties so may also be termed a photodiode. Photoresponsive deviceshave application as solar cells which generate electricity from lightand as photodetectors which measure or detect light.

The PV device comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) an anode (electrode),(f) a substrate.

The photoactive layer comprises the polymers of the present invention.Preferably, the photoactive layer is made of a conjugated polymer of thepresent invention, as an electron donor and an acceptor material, like afullerene, particularly a functionalized fullerene PCBM, as an electronacceptor. As stated above, the photoactive layer may also contain apolymeric binder. The ratio of the polymers of formula I to thepolymeric binder can vary from 5 to 95 percent. Preferably, thepolymeric binder is a semicristalline polymer such as polystyrene (PS),high-density polyethylene (HDPE), polypropylene (PP) andpolymethylmethacrylate (PMMA).

For heterojunction solar cells the active layer comprises preferably amixture of a polymer of the present invention and a fullerene, such as[60]PCBM (=6,6-phenyl-C₆₁-butyric acid methyl ester), or [70]PCBM, in aweight ratio of 1:1 to 1:3. The fullerenes useful in this invention mayhave a broad range of sizes (number of carbon atoms per molecule). Theterm fullerene as used herein includes various cage-like molecules ofpure carbon, including Buckminsterfullerene (C₆₀) and the related“spherical” fullerenes as well as carbon nanotubes. Fullerenes may beselected from those known in the art ranging from, for example,C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₀to C₉₆. Most preferably the fullerene is C₆₀ or C₇₀, such as [60]PCBM,or [70]PCBM. It is also permissible to utilize chemically modifiedfullerenes, provided that the modified fullerene retains acceptor-typeand electron mobility characteristics. The acceptor material can also bea material selected from the group consisting of any semi-conductingpolymer, such as, for example, a polymer of the present invention,provided that the polymers retain acceptor-type and electron mobilitycharacteristics, organic small molecules, carbon nanotubes, inorganicparticles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a polymer of the present invention asan electron donor and a fullerene, particularly functionalized fullerenePCBM, as an electron acceptor. These two components are mixed with asolvent and applied as a solution onto the smoothing layer by, forexample, the spin-coating method, the drop casting method, theLangmuir-Blodgett (“LB”) method, the ink jet printing method and thedripping method. A squeegee or printing method could also be used tocoat larger surfaces with such a photoactive layer. Instead of toluene,which is typical, a dispersion agent such as chlorobenzene is preferablyused as a solvent. Among these methods, the vacuum deposition method,the spin-coating method, the ink jet printing method and the castingmethod are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)(f) optionally an extra electrode to match the energy level,(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(h) a photoactive layer,(i) optionally a smoothing layer,(j) an anode (electrode),(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or filmscomprising the polymers of the present invention can also be used aloneor together with other materials in or as alignment layers in LCD orOLED devices, as described for example in US2003/0021913.

It is another object of the present invention to provide compounds,which show high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability, whenused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes.

In addition, the polymers of the present invention may be used as IRabsorbers.

Accordingly, the polymers of the present invention can be used interalia for security printing, invisible and/or IR readable bar codes, thelaser-welding of plastics, the curing of surface-coatings using IRradiators, the drying and curing of print, the fixing of toners on paperor plastics, optical filters for plasma display panels, laser marking ofpaper or plastics, the heating of plastics preforms, and for heatshielding applications.

In a further aspect, the invention provides a printing ink formulationfor security printing, comprising at least one polymer of the presentinvention, such as, for example, a polymer selected from P-1 to P-14 andP-16 to P-25.

In a further aspect, the invention provides a security document,comprising a substrate and at least at least one polymer, or compound ofthe present invention. The security document may be a bank note, apassport, a check, a voucher, an ID- or transaction card, a stamp and atax label.

In a further aspect, the invention provides a security document,obtainable by a printing process, wherein a printing ink formulation isemployed that comprises at least one polymer, or compound of the presentinvention.

Advantageously, the polymers, or compounds of the present invention,such as, for example, a polymer selected from P-1 to P-14 and P-16 toP-25, may be used in a printing ink formulation for security printing.

In security printing, the polymers, or compounds of the presentinvention are added to a printing ink formulation. Suitable printinginks are water-based, oil-based or solvent-based printing inks, based onpigment or dye, for inkjet printing, flexographic printing, screenprinting, intaglio printing, offset printing, laser printing orletterpress printing and for use in electrophotography. Printing inksfor these printing processes usually comprise solvents, binders, andalso various additives, such as plasticizers, antistatic agents orwaxes. Printing inks for offset printing and letterpress printing areusually formulated as high-viscosity paste printing inks, whereasprinting inks for flexographic printing and intaglio printing areusually formulated as liquid printing inks with comparatively lowviscosity.

The printing ink formulation, especially for security printing,according to the invention preferably comprises

-   -   a) at least one polymer, or compound of the present invention,        such as, for example, a polymer selected from polymers P-1 to        P-14 and P-16 to P-25,    -   b) a polymeric binder,    -   c) a solvent,    -   d) optionally at least one colorant, and    -   e) optionally at least one further additive.

Suitable components of printing inks are conventional and are well knownto those skilled in the art. Examples of such components are describedin “Printing Ink Manual”, fourth edition, Leach R. H. et al. (eds.), VanNostrand Reinhold, Wokingham, (1988). Details of printing inks and theirformulation are also disclosed in “Printing Inks”—Ullmann's Encyclopediaof Industrial Chemistry, Sixth Edition, 1999 Electronic Release. Aformulation of an IR-absorbing intaglio ink formulation is described inUS 20080241492 A1. The disclosure of the afore-mentioned documents isincorporated herein by reference.

The printing ink formulation according to the invention contains ingeneral from 0.0001 to 25% by weight, preferably from 0.001 to 15% byweight, in particular from 0.01 to 5% by weight, based on the totalweight of the printing ink formulation, of component a).

The printing ink formulation according to the invention contains ingeneral from 5 to 74% by weight, preferably from 10 to 60% by weight,more preferably from 15 to 40% by weight, based on the total weight ofthe printing ink formulation, of component b).

Suitable polymeric binders b) for the printing ink formulation accordingto the invention are for example selected from natural resins, phenolresin, phenol-modified resins, alkyd resins, polystyrene homo- andcopolymers, terpene resins, silicone resins, polyurethane resins,urea-formaldehyde resins, melamine resins, polyamide resins,polyacrylates, polymethacrylates, chlorinated rubber, vinyl esterresins, acrylic resins, epoxy resins, nitrocellulose, hydrocarbonresins, cellulose acetate, and mixtures thereof.

The printing ink formulation according to the invention can alsocomprise components that form a polymeric binder by a curing process.Thus, the printing ink formulation according to the invention can alsobe formulated to be energy-curable, e.g. able to be cured by UV light orEB (electron beam) radiation. In this embodiment, the binder comprisesone or more curable monomers and/oligomers. Corresponding formulationsare known in the art and can be found in standard textbooks such as theseries “Chemistry & Technology of UV & EB Formulation for Coatings, Inks& Paints”, published in 7 volumes in 1997-1998 by John Wiley & Sons inassociation with SITA Technology Limited.

Suitable monomers and oligomers (also referred to as prepolymers)include epoxy acrylates, acrylated oils, urethane acrylates, polyesteracrylates, silicone acrylates, acrylated amines, and acrylic saturatedresins. Further details and examples are given in “Chemistry &Technology of UV & EB Formulation for Coatings, Inks & Paints”, VolumeII: Prepolymers & Reactive Diluents, edited by G Webster.

If a curable polymeric binder is employed, it may contain reactivediluents, i.e. monomers which act as a solvent and which upon curing areincorporated into the polymeric binder. Reactive monomers are typicallychosen from acrylates or methacrylates, and can be monofunctional ormultifunctional. Examples of multifunctional monomers include polyesteracrylates or methacrylates, polyol acrylates or methacrylates, andpolyether acrylates or methacrylates.

In the case of printing ink formulations to be cured by UV radiation, itis usually necessary to include at least one photoinitiator to initiatethe curing reaction of the monomers upon exposure to UV radiation.Examples of useful photoinitiators can be found in standard textbookssuch as “Chemistry & Technology of UV & EB Formulation for Coatings,Inks & Paints”, Volume III, “Photoinitiators for Free Radical Cationicand Anionic Polymerisation”, 2nd edition, by J. V. Crivello & K.Dietliker, edited by G. Bradley and published in 1998 by John Wiley &Sons in association with SITA Technology Limited. It may also beadvantageous to include a sensitizer in conjunction with thephotoinitiator in order to achieve efficient curing.

The printing ink formulation according to the invention contains ingeneral from 1 to 94.9999% by weight, preferably from 5 to 90% byweight, in particular from 10 to 85% by weight, based on the totalweight of the printing ink formulation, of a solvent c).

Suitable solvents are selected from water, organic solvents and mixturesthereof. For the purpose of the invention, reactive monomers which alsoact as solvents are regarded as part of the afore-mentioned bindercomponent b).

Examples of solvents comprise water; alcohols, e.g. ethanol, 1-propanol,2-propanol, ethylene glycol, propylene glycol, diethylene glycol andethoxy propanol; esters, e.g. ethyl acetate, isopropyl acetate, n-propylacetate and n-butyl acetate; hydrocarbons, e.g. toluene, xylene, mineraloils and vegetable oils, and mixtures thereof.

The printing ink formulation according to the invention may contain anadditional colorant d). Preferably, the printing ink formulationcontains from 0 to 25% by weight, more preferably from 0.1 to 20% byweight, in particular from 1 to 15% by weight, based on the total weightof the printing ink formulation, of a colorant d).

Suitable colorants d) are selected conventional dyes and in particularconventional pigments. The term “pigment” is used in the context of thisinvention comprehensively to identify all pigments and fillers, examplesbeing colour pigments, white pigments, and inorganic fillers. Theseinclude inorganic white pigments, such as titanium dioxide, preferablyin the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic leadcarbonate, antimony trioxide, lithopones (zinc sulfide+barium sulfate),or coloured pigments, examples being iron oxides, carbon black,graphite, zinc yellow, zinc green, ultramarine, manganese black,antimony black, manganese violet, Paris blue or Schweinfurt green.Besides the inorganic pigments the printing ink formulation of theinvention may also comprise organic colour pigments, examples beingsepia, gamboge, Cassel brown, toluidine red, para red, Hansa yellow,indigo, azo dyes, anthraquinonoid and indigoid dyes, and also dioxazine,quinacridone, phthalocyanine, isoindolinone, and metal complex pigments.Also suitable are synthetic white pigments with air inclusions toincrease the light scattering, such as the Rhopaque® dispersions.Suitable fillers are, for example, aluminosilicates, such as feldspars,silicates, such as kaolin, talc, mica, magnesite, alkaline earth metalcarbonates, such as calcium carbonate, in the form for example ofcalcite or chalk, magnesium carbonate, dolomite, alkaline earth metalsulfates, such as calcium sulfate, silicon dioxide, etc.

The printing ink formulation according to the invention may contain atleast one additive e). Preferably, the printing ink formulation containsfrom 0 to 25% by weight, more preferably from 0.1 to 20% by weight, inparticular from 1 to 15% by weight, based on the total weight of theprinting ink formulation, of at least one component e).

Suitable additives (component e)) are selected from plasticizers, waxes,siccatives, antistatic agents, chelators, antioxidants, stabilizers,adhesion promoters, surfactants, flow control agents, defoamers,biocides, thickeners, etc. and combinations thereof. These additivesserve in particular for fine adjustment of the application-relatedproperties of the printing ink, examples being adhesion, abrasionresistance, drying rate, or slip.

In particular, the printing ink formulation for security printingaccording to the invention preferably contains

-   -   a) 0.0001 to 25% by weight of at least one polymer, or compound        of the present invention, such as, for example, a polymer        selected from polymers P-1 to P-14 and P-16 to P-25,    -   b) 5 to 74% by weight of at least one polymeric binder,    -   c) 1 to 94.9999% by weight of at least one a solvent,    -   d) 0 to 25% by weight of at least one colorant, and    -   e) 0 to 25% by weight of at least one further additive,    -   wherein the sum of components a) to e) adds up to 100%.

The printing ink formulations according to the invention areadvantageously prepared in a conventional manner, for example by mixingthe individual components.

Primers can be applied prior to the printing ink formulation accordingto the invention. By way of example, the primers are applied in order toimprove adhesion to the substrate. It is also possible to applyadditional printing lacquers, e.g. in the form of a covering to protectthe printed image.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight. Weight-average molecular weight (Mw) andpolydispersity (Mw/Mn=PD) are determined by Heat Temperature GelPermeation Chromatography (HT-GPC) [Apparatus: GPC PL 220 from Polymerlaboratories (Church Stretton, UK; now Varian) yielding the responsesfrom refractive index (RI), Chromatographic conditions: Column: 3 “PLgelOlexis” column from Polymer Laboratories (Church Stretton, UK); with anaverage particle size of 13 ím (dimensions 300×8 mm I.D.) Mobile phase:1,2,4-trichlorobenzene purified by vacuum distillation and stabilised bybutylhydroxytoluene (BHT, 200 mg/I), Chromatographic temperature: 150°C.; Mobile phase flow: 1 ml/min; Solute concentration: about 1 mg/ml;Injection volume: 200 íl; Detection: RI, Procedure of molecular weightcalibration: Relative calibration is done by use of a set of 10polystyrene calibration standards obtained from Polymer Laboratories(Church Stretton, UK) spanning the molecular weight range from 1′930′000Da-5′050 Da, i.e., PS 1′930′000, PS 1′460′000, PS 1′075′000, PS 560′000,PS 330′000, PS 96′000, PS 52′000, PS 30′300, PS 10′100, PS 5′050 Da. Apolynomic calibration is used to calculate the molecular weight.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions.

EXAMPLES Example 1 Synthesis of Polymer P-11

a) 7-bromo-9,9-di(2-methoxyethyl)-9H-fluorene-2-carbonitrile 2: Amixture of 2,7-dibromo-9H-fluorene (11.34 g, 35 mmol), potassium iodide(100 mg, 0.60 mmol) and 150 ml of THF is stirred under argon at roomtemperature. Sodium hydride (7.00 g, 175 mmol, 60% in mineral oil) iscarefully added in portions and the mixture is stirred for additional 15min. Subsequently 1-chloro-2-methoxyethane (9.6 ml, 105 mmol) is addeddropwise and the reaction mixture is stirred for 3 days at roomtemperature. The reaction is quenched by dropwise addition of 200 ml ofwater. The resulting black mixture is acidified with 6M HCl (colordisappeared) and extracted three times with methylene chloride. Combinedorganic layers are washed twice with water and dried over sodiumsulfate. Solvents are removed under reduced pressure and obtained solidresidue is recrystallized from ethanol to give 13.40 g (87%) of2,7-dibromo-9,9-di(2-methoxyethyl)-9H-fluorene 1 as a white powder. Mp:138-140° C. ¹H NMR (500 MHz, CDCl₃) δ 7.55 (d, J=1.4 Hz, 2H), 7.53 (d,J=8.1 Hz, 2H), 7.49 (dd, J=8.1, 1.7 Hz, 2H), 3.02 (s, 6H), 2.68 (dd,J=8.4, 6.7 Hz, 4H), 2.49-2.15 (m, 4H). ¹³C NMR (126 MHz, CDCl₃) δ 150.8,138.4, 130.8, 126.5, 121.8, 121.3, 68.1, 58.4, 51.7, 39.4. HRMS (EI)calcd for C₁₉H₂₀Br₂O₂ (M⁺): 437.9830. found: 437.9831.b) 2,7-Dibromo-9,9-di(2-methoxyethyl)-9H-fluorene 1 (13.21 g, 30 mmol),copper(I) cyanide (2.78 g, 31 mmol) and 100 ml of DMF are stirred underargon at 160° C. in a tightly closed pressure vessel. After 40 h thereaction mixture is cooled down and a solution of 26 g of FeCl₃.6H₂O in40 ml of concentrated hydrochloric acid and 10 ml of water is added.Resulting mixture is stirred for 20 min at 90° C., cooled down, dilutedwith water and extracted with 5 portions of methylene chloride. Organiclayers are combined, washed twice with water and dried over MgSO₄. Theproduct is purified by silica-gel chromatography(chloroform→chloroform:ethyl acetate 9:1) and recrystallized fromethanol. 5.20 g (45%) of 2 is obtained as off-white powder. Mp: 193-196°C. ¹H NMR (500 MHz, CDCl₃) δ 7.75 (dd, J=7.9, 0.6 Hz, 1H), 7.70 (dd,J=1.4, 0.6 Hz, 1H), 7.66 (dd, J=7.9, 1.4 Hz, 1H), 7.64-7.59 (m, 2H),7.55 (dd, J=8.1, 1.8 Hz, 1H), 2.99 (s, 6H), 2.78-2.70 (m, 2H), 2.70-2.62(m, 2H), 2.41-2.27 (m, 4H). ¹³C NMR (126 MHz, CDCl₃) δ 151.9, 149.6,143.8, 137.5, 131.9, 131.1, 127.0, 126.8, 123.4, 122.2, 120.5, 119.30,110.7, 68.0, 58.4, 52.0, 39.2. HRMS (ESI) calcd for C₂₀H₂₀BrNO₂Na(M+Na⁺): 408.0570. found: 408.0575.

DPP Synthesis

c)3,6-Bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole4: Under an argon atmosphere, in a three-necked flask equipped with areflux condenser and magnetic stirrer are placed 20 ml of tert-amylalcohol, an catalytic amount of iron(III) chloride and sodium (0.690 g,30 mmol). The mixture is heated under reflux until sodium is completelyreacted. Then the reaction mixture is cooled to 90° C. and7-bromo-9,9-di(2-methoxyethyl)-9H-fluorene-2-carbonitrile (2, 4.87 g,12.6 mmol) is added. The mixture is then heated to 110° C. and 1.23 ml(6.0 mmol) of diisopropyl succinate 3 is added dropwise (30 min). After16 h of reaction at 110° C., the mixture is cooled and 30 ml ofwater/acetic acid 1:1 is added. Resulting suspension is refluxed for afew minutes and cooled to 30° C. Precipitate of obtained pigment is thenfiltered out, washed several times with hot water and methanol and driedunder vacuum. 1.66 g (32%) of 4 is obtained as dark brown powder.Mp: >400° C. ¹H NMR (500 MHz, CDCl₃: TFA-d 4:1) δ 8.48 (br s, 2H), 8.22(br s, 2H), 7.96 (br s, 2H), 7.72 (d, J=8.0 Hz, 2H), 7.69-7.62 (m, 4H),3.17 (s, 6H), 3.11-2.95 (m, 8H), 2.59 (br s, 4H), 2.50 (br s, 4H). HRMS(ESI) calcd for C₄₄H₄₂Br₂N₂O₆Na (M+Na⁺): 875.1301. found: 875.1307.

Synthesis of Diacetal

d)2,5-Bis(2,2-diethoxyethyl)-3,6-bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole5: A mixture of3,6-Bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole(4, 684 mg, 0.80 mmol), tetrabutylammonium bisulfate (TBAHS, 14 mg, 0.04mmol), potassium carbonate (1.66 g, 12 mmol) and 20 ml of DMF is heatedto 130° C. under an argon atmosphere. Then bromoacetaldehyde diethylacetal (1.20 ml, 8.0 mmol) is added dropwise by a syringe (30 min). Thereaction mixture is stirred for 16 h at 130° C., cooled and diluted withwater and methylene chloride. The aqueous layer is extracted with fiveportions of methylene chloride, combined organic layers are washed withwater and brine and dried over sodium sulfate. Solvents are evaporated,the product is separated by the column chromatography (methylenechloride:acetone 19:1→9:1) and recrystallized from CHCl₃/MeOH. 440 mg(51%) of 5 is obtained as orange-yellow fluorescent powder. Mp: 197-199°C. ¹H NMR (500 MHz, CDCl₃) δ 8.23 (d, J=1.1 Hz, 2H), 8.16 (dd, J=8.0,1.5 Hz, 2H), 7.82 (d, J=8.0 Hz, 2H), 7.65-7.60 (m, 4H), 7.53 (dd, J=8.2,1.7 Hz, 2H), 4.97 (t, J=5.6 Hz, 2H), 3.90 (d, J=5.6 Hz, 4H), 3.73 (dq,J=9.3, 7.0 Hz, 4H), 3.55 (dq, J=9.4, 7.0 Hz, 4H), 3.05 (s, 12H),2.85-2.73 (m, 8H), 2.45 (ddd, J=15.0, 9.5, 5.7 Hz, 4H), 2.34 (ddd,J=13.5, 9.6, 5.4 Hz, 4H), 1.19 (t, J=7.0 Hz, 12H). ¹³C NMR (126 MHz,CDCl₃) δ 163.4, 152.1, 149.1 (2 signals), 142.3, 138.5, 130.9, 129.7,127.1, 126.8, 124.3, 122.5, 121.8, 120.3, 109.6, 100.4, 68.3, 63.8,58.4, 51.8, 45.8, 39.3, 15.5. HRMS (ESI) calcd for C₅₆H₆₆Br₂N₂O₁₀Na(M+Na⁺): 1107.2982. found: 1107.3010.

Cyclization of Acetal

e)2,5-Bis(2,2-diethoxyethyl)-3,6-bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole(6=compound 1-8): (5, 435 mg, 0.40 mmol) is dissolved in 8 ml ofchloroform. Subsequently trifluoromethanesulfonic acid (0.78 ml, 8.8mmol) is slowly added and the reaction mixture is stirred at 60° C. for1 h. Then the reaction mixture is cooled down and triethyl amine (1.4ml, 10 mmol) is slowly added in order to neutralize acid. Obtained darkblue mixture is diluted with methylene chloride, washed 3 times withwater and dried over sodium sulfate. Solvents are evaporated and thesolid residue is recrystallized from CHCl₃/MeOH. 329 mg (91%) of 6 isobtained as dark violed crystals. Mp: 354-356° C. ¹H NMR (500 MHz,CDCl₃) δ 9.26 (s, 2H), 7.91 (d, J=7.3 Hz, 2H), 7.84 (s, 2H), 7.70 (d,J=8.1 Hz, 2H), 7.67 (d, J=1.4 Hz, 2H), 7.57 (dd, J=8.1, 1.8 Hz, 2H),6.88 (d, J=7.3 Hz, 2H), 3.01 (s, 12H), 2.92-2.78 (m, 8H), 2.61 (ddd,J=14.5, 8.9, 5.7 Hz, 4H), 2.40 (ddd, J=14.1, 9.0, 5.5 Hz, 4H). ¹³C NMR(126 MHz, CDCl₃) δ 155.8, 152.7, 150.0, 144.4, 141.4, 137.8, 134.6,131.1, 127.2, 124.1, 123.6, 123.2, 122.7, 122.3, 117.4, 112.3, 101.5,68.4, 58.3, 51.9, 39.5. HRMS (ESI) calcd for C₄₈H₄₂Br₂N₂O₆ (M⁺):900.1410. found: 900.1396.

f) (compound 7=Polymer P-11) One equivalent of compound 6 and oneequivalent of the thiophene-bis-boronicacidester [175361-81-6] arecopolymerized under Suzuki reaction conditions to get the polymer P-11.

Example 2 Synthesis of Polymer P-2

a) The synthesis of the monomer 10 is made according to Org. Lett. 2012,p. 2670: the DPP pigment 8 [84632-54-2] is reacted with 2 equivalents ofphenacyl bromide [70-11-1] and a base to get the alkylated DPP 9:

b) The ring closure to compound 10 is made under acidic conditions:

c) The polymer P-2 is then made by Suzuki co-polymerization of 1equivalent of compound 10 and one equivalent of the diboronicacidester11 using the polymerisation conditions of example 1f):

Example 3 Synthesis of Polymer P-12 (Compound 18)

a) Compound 14 is synthesized according to compound 2:

Compound 14 can be alternatively synthesized by the following route:

Synthesis of 9H-Fluorene-2-carbonitrile [2523-48-0]

Under an argon atmosphere, in a three-necked flask (250 mL) are placed2-bromo-9H-fluorene ([1133-80-8], 37.86 g, 0.15 mol), copper(I)cyanide(21.68 g, 0.242 mol) and dimethylformamide (190 mL). Resultingsuspension is heated to reflux under argon. The reaction mixture isstirred at 152° C. (oil bath 165° C.) for 17 h under argon. The reactionmixture is cooled to room temperature and then poured into cold waterwith ammonium hydroxide (600 mL cold water with ice, 200 mL 25% NH₄OHaq) and stirred for 2 h. The light brownish precipitate formed iscollected by filtration. The solids are washed with dilute ammoniumhydroxide (800 mL) and then with water (800 mL) to get the crudeproduct. The wet product is washed from the funnel (6×100 mL)dichloromethane and the combined organic phases are washed with water(200 mL), NaCl sat. (50 mL) and dried over Na₂SO₄ (40.0 g). After that,the Na₂SO₄ is filtered off, washed with methylene chloride (2×50 mL).The solvent is evaporated. The raw product [2523-48-0] is dried undervacuum at 40° C. for 2 h. Yield 28.58 g (99.6%). M.p. 88-90° C. Thecrude product is used to the next step without purification.

Synthesis of 7-bromo-9H-fluorene-2-carbonitrile [656238-34-5]

To a stirred solution of 9H-fluorene-2-carbonitrile (25.39 g, 0.132 mol)in CH₂Cl₂ (200 mL) is added Br₂ (27.2 mL, 0.53 mol, 4.0 eq). The HBrevolved from solution is guided through a trap to a scrubbing solutionof NaOH. The mixture is stirred for 16 h. The yellow precipitate isfiltered off, washed with 5% NaHSO₃ (500 mL), water (4×500 mL) and isdried on an evaporator at 50° C. for 1 h and overnight at roomtemperature in vacuum (oil pump). The crude grey solid is isolated.Yield 16.45 g 45.8%

The filter funnel is washed with 200 mL of dichloromethane and combinedwith the filtrate. After separation the water layer is extracted withdichloromethane (200 mL). The combined organic layers are washed withwater (4×400 mL) brine (100 mL) and dried over Na₂SO₄. The drying agentis filtered off (wash 100 mL CH₂C₁₂) and after evaporation of solventthe residue is died under vacuum. Yield 17.46 g 48.6% Total yield 94.4%of product [656238-34-5]. M.p. 166-173° C., lit m.p. 172° C.

Synthesis of 7-bromo-9,9-dioctyl-9H-fluorene-2-carbonitrile[428865-55-8]

27.2 g (0.1 mol) of 7-Bromo-9H-fluorene-2-carbonitrile and potassiumiodide (0.9 g) are dissolved in 150 mL of dimethyl sulfoxide underargon. The solution is cooled to 10° C. and 1-bromooctane (44.6 g, 0.23mol) is added dropwise and potassium hydroxide (34.0 g 0.6 mol) is addedin small portions under argon. The temperature is monitored to be under20° C. Afterwards the reaction mixture is stirred overnight at roomtemperature. The mixture is diluted with diethyl ether (250 mL), thenfiltered through celite (40.0 g) and washed with diethyl ether (150 mL,50 mL). The filtrate is poured into de-ionized water with ice (500 mL).The organic phases are collected and washed with water (3×100 mL), brine(50 mL) and dried over sodium sulphate (50 g). The solution is filteredthrough celite (50.0 g) and silica (80 g), washed with diethyl ether(3×100 mL) and concentrated to give the crude product as yellow oil(51.86 g). Product is isolated by recrystallization from a mixture ofmethanol (80 mL), isopropanol (10 mL) and diethyl ether (2 mL) to giveproduct [428865-55-8]. Yield 33.89 g (68.1%), m.p.: 50.0-54.0° C. lit.mp. 48.3-52.2° C., ¹H NMR (500 MHz, CDCl₃) δ: 7.74 (dd, J=7.9, 0.5 Hz,1H), 7.58-7.68 (m 3H), 7.49-7.53 (m, 2H), 1.95 (ddd, J=9.5, 6.3, 2.8 Hz,4H, CH₂CH₂(CH₂)₅CH₃), 1.03-1.25 (m, 20H, CH₂CH₂(CH₂)₅CH₃), 0.83 (t,J=7.2 Hz, 6H, CH₂CH₂(CH₂)₅CH₃), 0.55 (m, 4H, CH₂CH₂(CH₂)₅CH₃).

DPP Synthesis

b) Reaction flask (250 mL) is charged with 40 ml 2-methyl-2-butanol, 2.0g (86.9 mmol) sodium, and 30 mg iron(III)chloride under argon. Thereaction mixture is heated to 100° C. under argon. The reaction mixtureis stirred 1 h to the moment when all sodium is dissolved. Then thereaction mixture is cooled to 90° C. and7-bromo-9,9-dioctyl-9H-fluorene-2-carbonitrile (10.14 g, 20.5 mmol) isadded in one portion (wash with 20 ml of 2-methyl-2-butanol). Thereaction is stirred for 10 minutes, warmed up to 110° C. and 1.98 g(9.79 mmol) diisopropyl succinate is added via syringe. The reactionmixture is stirred in an oil bath at 110° C. under argon overnight. Nextday the reaction mixture is cooled to 60° C., quenched by addition of 25mL AcOH, 25 mL water and 25 mL EtOH. After 1 h at 100° C. the stirringis continued overnight at RT. Next day 100 mL of water are added and theraw product is filtered on G3 filter. To the residue filter cake water(25 mL) and EtOH (600 mL) are added in small portions, then the productis isolated by filtration and dried at room temperature under vacuum(oil pump). Yield 2.49 g (23.7%) of a compound of formula 15. Thiscompound is directly used in the next reaction to give compound 16.

Synthesis of Diacetal

c) A mixture of3,6-bis(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole(1.24 g, 1.16 mmol), potassium carbonate (2.40 g, 17.4 mmol) and 25 mlof NMP is heated to 120° C. under an argon atmosphere. Thenbromoacetaldehyde diethyl acetal (1.70 ml, 10.0 mmol) is added by asyringe. The reaction mixture is stirred for 1 h at 120° C. then secondportion of bromoacetaldehyde diethyl acetal (1.70 ml, 10.0 mmol) isadded by a syringe and the reaction is continued over night at 130° C.Next day the reaction mixture is cooled and quenched with water. Theproduct is extracted with three portions of hexane. The combined organiclayers are washed twice with water and brine. Finally dried over sodiumsulfate, solvents are evaporated and the product is purified by columnchromatography (hexane:ethyl acetate 29:1→19:1). 0.723 g (48%) of acompound of formula 16 are obtained as red-orange fluorescent solidafter drying overnight in vacuum (oil pump).

Cyclization of Acetal (Compound (I-9))

d) The diacetal,3,6-bis(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-2,5-bis(2,2-diethoxyethyl)-1,4-diketopyrrolo-[3,4-c]pyrrole(677 mg, 0.519 mmol), is dissolved in 10 ml of chloroform under an argonatmosphere. Subsequently trifluoromethanesulfonic acid (0.92 ml, 10.4mmol) is slowly added and the reaction mixture is stirred at 60° C. for1 h. Then the reaction mixture is cooled down and a solution of triethylamine (1.75 ml, 12.6 mmol) in 5 ml of CHCl₃ is slowly added in order toneutralize the acid. The obtained dark blue mixture is placed in a 500ml Erlenmeyer flask and 200 ml of EtOH are added. The resultingsuspension is cooled down and the precipitate is filtered off and driedunder vacuum to give a compound of formula 17 (=compound (I-9) as darkblue powder. Yield: 536 mg (92%).

¹H NMR (500 MHz, CDCl₃) δ 9.19 (s, 2H, 9-H and 20-H), 7.91 (d, J=7.3 Hz,2H, 1-H and 12-H), 7.83 (s, 2H, 3-H and 14-H), 7.70 (d, J=7.9 Hz, 2H,4-H and 15-H), 7.59-7.50 (m, 4H, 7-H and 18-H+, 5-H and 16-H), 6.88 (d,J=7.4 Hz, 2H, 2-H and 13-H), 2.29-2.15 (m, 4H, CH₂CH₂(CH₂)₅CH₃),2.12-1.98 (m, 4H, CH₂CH₂(CH₂)₅CH₃), 1.32-0.94 (m, 40H, CH₂CH₂(CH₂)₅CH₃),0.78 (t, J=7.1 Hz, 12H, CH₂CH₂(CH₂)₅CH₃), 0.72-0.62 (m, 8H,CH₂CH₂(CH₂)₅CH₃).

Polymerization

The polymer P-12 (compound 18) is obtained according to polymer P-11 viaSuzuki-polymerization reaction of compound 17 and compound[924894-85-9].

Example 4 Synthesis of Polymer P-21 (Compound 19)

500 mg of compound 17 and 186.8 mg of compound [239075-02-6] are addedunder argon to 25 ml of tetrahydrofuran. Then 48.24 mg of the phosphineligand [740815-37-6] are added together with 8 mg ofpalladium(II)acetate. Then the mixture is heated to reflux. Then 112.47mg of LiOH monohydrate is added and the mixture is heated at refluxovernight. The mixture is cooled and poured into water. The precipitateis filtered and washed with water and methanol. The filter cake is thenSoxhlet extracted with heptane, tetrahydrofuran and toluene. Thetetrahydrofurane fraction contains a polymer 19 having a weight-averagemolecular weight (M_(w)) of 20′246 Da and a polydispersity (PDI) of2.52. The toluene fraction contains a polymer 19 having M_(w) of 28′825Da and PDI of 1.72.

Example 5 Synthesis of Polymer P-22 (Compound 20)

The polymer P-22 (compound 20) is obtained in analogy to polymer P-21(compound 19) via Suzuki-polymerization reaction of compound 17 andcompound [175361-81-6]. The tetrahydrofurane fraction contains a polymer20 having a M_(w) of 27′769 Da and a PDI of 2.04. The toluene fractioncontains a polymer 20 having a M_(w) of 54′561 Da and a PDI of 1.70.

Example 6 Synthesis of Compound 21 (P-23)

1000 mg of compound 17 and 520.76 mg of the tin compound [14275-61-7]are added to dry toluene under argon. Then 29.78 mg oftetrakis(triphenylphosphine)palladium are added and the mixture isheated to reflux overnight. The reaction mixture is cooled and pouredinto methanol. The precipitate is filtered and the filter cake is washedwith methanol and acetone. The filter cake is then Soxhlet extractedwith heptane, tetrahydrofuran and toluene. The tetrahydrofurane fractioncontains a polymer 21 having a M_(w) of 30′484 Da and a PDI of 3.14. Thetoluene fraction contains a polymer 21 having a M_(w) of 65′063 Da and aPDI of 2.83.

Example 7 Synthesis of Compound 25 (I-16)

a) Synthesis of compound 22 is made in analogy to the synthesis ofcompound 14 by the alkylation of compound [656238-34-5] with1-bromo-dodecane.

¹H NMR (500 MHz, CDCl₃) δ: 7.73 (d, J=7.8 Hz, 1H), 7.63 (dd, J=7.9, 1.2Hz, 1H), 7.61-7.58 (m, 3H), 7.49-7.52 (m 2H), 1.95 (ddd, J=9.9, 6.4, 2.8Hz, 4H, CH₂CH₂(CH₂)₉CH₃), 1.30-1.10 (m, 36H, CH₂CH₂(CH₂)₉CH₃), 0.83 (t,J=7.1 Hz, 6H, CH₂CH₂(CH₂)₉CH₃), 0.55 (m, 4H, CH₂CH₂(CH₂)₉CH₃).

Synthesis of Compound 23

b) Synthesis of compound 23 is made in analogy to the synthesis ofcompound 15 by the condensation reaction of compound 22 and compound 3.

¹H NMR (500 MHz, CDCl₃: TFA-d 4:1) δ 8.41 (br s, 2H, 1-H at fluorenyl),8.20 (br d, J=6.4 Hz, 2H, 3-H at fluorenyl), 7.90 (d, J=7.9 Hz, 2H, 4-Hat fluorenyl), 7.72-7.56 (m, 6H, 5-H, 6-H and 8-H at fluorenyl), 2.19(td, J=10.0, 3.8 Hz, 4H, CH₂CH₂(CH₂)₉CH₃), 2.08 (td, J=10.0, 3.8 Hz, 4H,CH₂CH₂(CH₂)₉CH₃), 1.38-0.96 (m, 72H, CH₂CH₂(CH₂)₉CH₃), 0.86 (t, J=6.2Hz, 12H, CH₃), 0.82-0.64 (m, 8H, CH₂CH₂(CH₂)₉CH₃).

Synthesis of Compound 24

c) Synthesis of compound 24 is made in analogy to the synthesis ofcompound 16 by the alkylation of compound 23 with bromoacetaldehydediethyl acetal.

¹H NMR (500 MHz, CDCl₃) δ: 8.16 (s, 2H), 8.15 (dd, J=7.9, 1.2 Hz, 1H,),7.80 (d, J=7.9 Hz, 1H,), 7.61 (d, J=7.9 Hz, 1H), 7.47-7.60 (m 3H),).4.99 (t, J=5.6 Hz, 2H, NCH₂CH(OEt)₂), 3.90 (d, J=5.8 Hz, 4H,NCH₂CH(OEt)₂), 3.73 (dq, J=9.5, 7.1 Hz, 4H, OCH₂CH₃), 3.55 (dq, J=9.2,7.0 Hz, 4H, OCH₂CH₃), 2.05 (ddd, J=13.4, 10.1, 6.4 Hz, 4H,CH₂CH₂(CH₂)₉CH₃), 1.96 (ddd, J=13.4, 10.1, 6.4 Hz, 4H, CH₂CH₂(CH₂)₉CH₃),1.00-1.30 (m, 96H, CH₂CH₂(CH₂)₉CH₃ and OCH₂CH₃), 0.85 (t, J=7.0 Hz, 12H,CH₂CH₂(CH₂)₉CH₃), 0.62-0.71 (m, 8H, CH₂CH₂(CH₂)₉CH₃).

Synthesis of Compound 25 (I-16)

d) Synthesis of compound 25 is made in analogy to the synthesis ofcompound 17 by ring closing reaction of compound 24 under acidicconditions.

¹H NMR (500 MHz, CDCl₃) δ 9.19 (s, 2H, 9-H and 20-H), 7.91 (d, J=6.7 Hz,2H, 1-H and 12-H), 7.83 (s, 2H, 3-H and 14-H), 7.69 (d, J=7.9 Hz, 2H,4-H and 15-H), 7.60-7.50 (m, 4H, 7-H and 18-H+, 5-H and 16-H), 6.87 (d,J=7.3 Hz, 2H, 2-H and 13-H), 2.28-2.18 (m, 4H, CH₂CH₂(CH₂)₉CH₃),2.09-1.98 (m, 4H, CH₂CH₂(CH₂)₉CH₃), 1.24-1.00 (m, 72H, CH₂CH₂(CH₂)₉CH₃),0.82 (t, J=7.1 Hz, 12H, CH₂CH₂(CH₂)₉CH₃), 0.73-0.63 (m, 8H,CH₂CH₂(CH₂)₉CH₃).

Example 8 Synthesis of Compound 26 (P-24)

The polymer P-24 (compound 26) is obtained in analogy to polymer P-21(compound 19) via Suzuki polymerization reaction of compound 25 andcompound [175361-81-6]. The tetrahydrofuran fraction contains a polymer26 having a M_(w) of 44′416 Da and a PDI of 1.73.

Example 8 Synthesis of Compound 27 (P-25)

The polymer P-25 (compound 27) is obtained in analogy to polymer P-23(compound 21) via Stille polymerization reaction of compound 25 andcompound [14275-61-7]. The tetrahydrofuran fraction contains a polymer27 having a M_(w) of 124′676 Da and a PDI of 4.58.

Application Example 1 Fabrication and Electrical Characterization of anOrganic Field-Effect Transistor (OFET) Based on Polymer P-22 Preparationof Bottom-Contact, Top-Gate FETs

Polymer P-22 is dissolved at a concentration of 0.75 wt % in toluene andsubsequently coated onto a PET-substrate with lithographically patternedgold contacts, serving as Source and Drain contact of the OFET. 100 μlof the formulation is coated by a standard blade coater at a coatingspeed of 20 mm/s, yielding a homogenous layer of the semiconductor overthe entire substrate. After the coating is completed, the substrate isimmediately transferred onto a preheated hotplate and heated for 30 s at90° C. Next the gate dielectric layer consisting of Cytop CTL-809M isspin coated on top of the organic semiconductor (1200 rpm, 30 s). Afterspin coating, the substrate is again transferred to the hotplate andannealed for another 5 Min at 100° C. Finally 50 nm thick shadow-maskpatterned gold gate electrodes are deposited by vacuum evaporation tocomplete FETs in the BGTC-configuration.

With the channel length L=10 μm and the channel width W=250 μm, the holemobility is calculated to μ˜1×10⁻⁴ cm²/Vs for this representativedevice. The threshold voltage is −6.5V, for the ON/OFF ratio is1.06×10².

Application Example 2 Fabrication and Electrical Characterization of anOrganic Field-Effect Transistor (OFET) Based on Polymer P-25

The sample preparation and electrical characterization is identical tothe description in Application Example 1.

With the channel length L=10 μm and the channel width W=250 μm, the holemobility is calculated to μ˜4×10⁻⁵ cm²/Vs for this representativedevice. The threshold voltage is −8V, for the ON/OFF ratio is 1.1×10¹.

Application Example A3

A solution of polymer P-21 in toluene is bladed on a top gate bottomcontact transistor (gold contacts, channel length 100 μm and 200 μm,channel width 10000 μm). Cytop is used as dielectric. A hole mobility of0.001 cm²/Vs is measured for both channel lengths.

1. A polymer, comprising one or more (repeating) unit(s) of formula

wherein Y is of formula

a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1,2, or 3; c is 0, 1, 2, or 3; and c′ is 0, 1, 2, or 3; Ar and Ar′ denotea homo- or heteroaromatic system, which may be substituted, orunsubstituted; R¹, R^(1′), R² and R^(2′) may be the same or differentand are selected from hydrogen, a C₁-C₁₀₀alkyl group which canoptionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group;and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—,NR³⁹CO—, —COO—, —CO— or —OCO—, a C₂-C₁₀₀alkenyl group which canoptionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group;and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—,NR³⁹CO—, —COO—, —CO— or —OCO—, a C₃-C₁₀₀alkinyl group which canoptionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group;and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—,NR³⁹CO—, —COO—, —CO— or —OCO—, a C₃-C₁₂cycloalkyl group which canoptionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group;and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—,NR³⁹CO—, —COO—, —CO— or —OCO—, a C₆-C₂₄aryl group which can optionallybe substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy,halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; aC2-C20heteroaryl group which can optionally be substituted one or moretimes with C1-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group,or —COO—C₁-C₁₈alkyl group; R³⁹ is hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl, Ar¹, Ar^(1′), Ar²,Ar^(2′), Ar³ and Ar^(3′) are independently of each other

such as, for example,

wherein X is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R⁷)—, —C(═O)—,

wherein X¹ is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—,—Ge(R¹¹⁷)(R^(117′))—C(R¹⁰⁸)(R¹⁰⁹)—, —C(═O)—,

R³ and R^(3′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, CF₃, cyano, C₁-C₂₅alkyl, C₃-C₂₅alkyl, which isoptionally interrupted by one or more oxygen or sulphur atoms;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R⁴, R^(4′), R⁵, R^(5′), R⁶ and R^(6′)are independently of each other hydrogen, halogen, halogenatedC₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which is optionally interrupted by one or more oxygen or sulphur atoms;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) areindependently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl, which isoptionally interrupted by one, or more oxygen, or sulphur atoms; orC₇-C₂₅arylalkyl, R⁸ and R^(8′) are independently of each other hydrogen,C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; or C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which isoptionally interrupted by one or more oxygen or sulphur atoms; orC₇-C₂₅arylalkyl, R¹¹ and R^(11′) are independently of each otherC₁-C₂₅alkyl group, especially a C₁-C₈alkyl group, C₇-C₂₅arylalkyl, or aphenyl group, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are independently of eachother hydrogen, halogen, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which is optionally interrupted by one, or more oxygen, or sulphuratoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

, wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group;R¹⁰⁴ and R^(104′) are independently of each other hydrogen, C₁-C₁₈alkyl,cyano, COOR¹⁰³, C₆-C₁₀aryl, which may optionally be substituted by G, orC₂-C₈heteroaryl, which is optionally substituted by G, R¹⁰³ and R^(103′)are independently of each other C₁-C₁₀₀alkyl, especially C₃-C₂₅alkyl,C₁-C₂₅alkyl substituted by E and/or interrupted by D, C₇-C₂₅arylalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G, R¹⁰⁵, R^(105′), R¹⁰⁶, andR^(106′) are independently of each other hydrogen, halogen, cyano,C₁-C₂₅alkyl, which is optionally interrupted by one or more oxygen orsulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy, R¹⁰⁷ is hydrogen,C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl; C₁-C₂₅alkyl;C₃-C₂₅alkyl, which may be interrupted by —O—, or —S—; or —COOR¹⁰³; R¹⁰³is as defined above; R¹⁰⁸ and R¹⁰⁹ are independently of each other H,C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted byD, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁸ andR¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six memberedring, which optionally is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl whichis substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl, D is —CO—, —COO—, —S—, —O—, or —NR¹¹²—, E isC₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³ or halogen, Gis E, or C1-C18alkyl, and R¹¹² and R¹¹³ are independently of each otherH; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R¹¹⁴ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which is optionallyinterrupted by one, or more oxygen, or sulphur atoms, R¹¹⁵ and R^(115′)are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which is optionally interrupted by one, or moreoxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₅alkyl)silyl group;R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group, aC₁-C₈alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸,R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹²² and R^(122′)are independently of each other hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which is optionally interrupted by one or moreoxygen or sulphur atoms; or C₇-C₂₅arylalkyl.
 2. The polymer according toclaim 1, comprising one or more units of formula

wherein Y is of formula

wherein a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; wherein Ar¹, Ar^(1′),Ar and Ar′ and R¹, R^(1′), R² and R^(2′) are as defined in claim
 18. 3.The polymer according to claim 1, comprising one or more units offormula

wherein R¹, R^(1′), R² and R^(2′) may be the same or different and areselected from hydrogen or a C₁-C₃₈alkyl group; R⁹¹, R^(91′) and R^(91″)are independently of each other H, halogen, especially F; cyano,C₁-C₂₅alkoxy, C₁-C₂₅alkyl substituted with one or more halogen atoms,especially F; or C₁-C₂₅alkyl, R⁹² is H, halogen, especially F; cyano,C₁-C₂₅alkoxy, or C₁-C₂₅alkyl, R⁹⁴ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, halogen, F; or C₁-C₁₈alkoxy;C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms and/or is optionally substituted by one or more halogenatoms, F; or C₇-C₂₅arylalkyl; and R^(99′″) is hydrogen, C₁-C₂₅alkyl, orC₁-C₂₅alkyl substituted with one or more halogen atoms and/orinterrupted by one or more oxygen atoms, or two groups R⁹⁹ can form a 5or 6 membered alkyl ring; or is one or more units of formula

wherein R¹, R^(1′), R² and R^(2′) may be the same or different and areselected from hydrogen or a C₁-C₃₈alkyl group; R⁹⁹, R^(99′), R^(99″) andR^(99*) are independently of each other hydrogen, C₁-C₂₅alkyl, orC₁-C₂₅alkyl interrupted by one or more oxygen atoms; C₃-C₂₅alkyl, orC₃-C₂₅alkyl which is interrupted by one or more oxygen atoms; R¹²¹,R¹²², R¹²³, R¹²⁴ and R¹²⁵ are independently of each other hydrogen,halogen, C₁-C₁₈alkoxy or C₁-C₂₅alkyl; preferably hydrogen; and R¹³⁰ ishydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,halogen, F; or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, which is optionallyinterrupted by one or more oxygen or sulphur atoms and/or is optionallysubstituted by one or more halogen atoms, F; or C₇-C₂₅arylalkyl.
 4. Thepolymer according to claim 3, comprising one or more units of formula

wherein R¹ and R^(1′) may be the same or different and are selected fromhydrogen, or a C₁-C₃₈alkyl group; R⁹¹ is H, F; cyano, C₁-C₂₅alkoxy,C₁-C₂₅alkyl substituted with one or more F; or C₁-C₂₅alkyl, R⁹⁹ ishydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with one or morehalogen atoms and/or interrupted by one or more oxygen atoms, or twogroups R⁹⁹ form a 5 or 6 membered alkyl ring.
 5. The polymer accordingto claim 1, comprising units of formula

wherein A is a repeating unit of formula (I), and -COM¹- is a repeatingunit, which has the meaning of Ar¹, wherein Ar¹ is as defined in claim1, or is of formula

s is 1, t is 1, u is 0, or 1, v is 0, or 1, and Ar¹⁴, Ar¹⁵, Ar¹⁶ andAr¹⁷ are independently of each other a group of formula

wherein one of X⁵ and X⁶ is N and the other is CR¹⁴, and R¹⁴, R^(14′),R¹⁷ and R^(17′) are independently of each other H, or a C₁-C₂₅alkylgroup.
 6. The polymer according to claim 5, which is a polymer offormula

wherein A and COM¹ are as defined in claim 5; and n is 4 to
 1000. 7.-17.(canceled)
 18. The polymer according to claim 5, wherein A is arepeating unit of formula (Ya), (Yb), (Yd), (Yj), (Yo), (Yo*), (Yaf),(Yah), (Ya′), (Yb′), (Yd′), (Yj′), (Yo′), (Yaf′), or (Yah′)

is of formula

where R³, R^(3′), R¹⁷ and R^(17′) are independently of each otherhydrogen, or C₁-C₂₅alkyl, and R¹⁰⁴ and R^(104′) are independently ofeach other hydrogen, cyano or a C₁-C₂₅alkyl group, and R¹⁰⁸ and R¹⁰⁹ areindependently of each other a C₁-C₂₅alkyl, which may be interrupted byone or more oxygen atoms.
 19. The polymer according to claim 18including a repeat unit of formula

and n is 4 to
 1000. 20. The polymer according to claim 5, wherein

is of formula

wherein R¹⁰⁸ and R¹⁰⁹ are independently of each other a C₁-C₂₅alkyl,which may be interrupted by one or more oxygen atoms.
 21. The polymeraccording to claim 19, wherein

is of formula

wherein R¹⁰⁸ and R¹⁰⁹ are independently of each other a C₁-C₂₅alkyl,which may be interrupted by one or more oxygen atoms.
 22. The polymeraccording to claim 5, which is of formula

wherein n is 4 to 1000, R¹ and R² are independently of each otherhydrogen, a phenyl group, which is optionally substituted by one, ormore C₁-C₁₈alkyl groups, or a C₁-C₃₈alkyl group, R³ and R^(3′) areindependently of each other hydrogen, or C₁-C₂₅alkyl; R¹² and R^(12′)are independently of each other hydrogen, F, cyano, C₁-C₂₅alkyl, or

, and R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; R¹⁷and R^(17′) are independently of each other H, or a C₁-C₂₅alkyl group;R⁹¹, R^(91′) and R^(91″) are independently of each other H, halogen, F;cyano, C₁-C₂₅alkoxy, C₁-C₂₅alkyl substituted with one or more halogenatoms or C₁-C₂₅alkyl, R⁹² is H, halogen, F, cyano, C₁-C₂₅alkoxy, orC₁-C₂₅alkyl, and R⁹⁹ and R^(99′) are independently of each otherhydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with one or morehalogen atoms and/or interrupted by one or more oxygen atoms, or twomoieties R⁹⁹ form a 5 or 6 membered alkyl ring.
 23. The polymeraccording to claim 22 which is of formula

wherein n is 4 to
 1000. 24. An organic semiconductor material, layer orcomponent, comprising a polymer according to claim
 1. 25. Asemiconductor device comprising a polymer according to claim
 1. 26. Asemiconductor device comprising an organic semiconductor material layeror component according to claim
 24. 27. The semiconductor deviceaccording to claim 25, which is an organic photovoltaic device, aphotodiode, or an organic field effect transistor.
 28. Process for thepreparation of an organic semiconductor device, the process comprisingproviding a solution and/or dispersion of a polymer according to claim 1in an organic solvent, applying the solution and/or dispersion to asuitable substrate, and removing the solvent.
 29. A compound of formula

wherein X² and X^(2′) are independently of each other halogen, Br, or J,ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, and R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical ordifferent, and are H or C₁-C₆alkyl, wherein two radicals optionally forma common ring and these radicals are optionally branched or unbranched,—SiR²¹⁰R²¹¹R²¹², and R²¹⁰, R²¹¹ and R²¹² are identical or different, andare halogen or C₁-C₆alkyl; X¹² is a halogen atom, I, or Br; —OS(O)₂CF₃,—OS(O)₂-aryl, —B(OH)₂, —B(OY¹)₂, —OS(O)₂CH₃,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group, —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, whereinY³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of eachother hydrogen, or a C₁-C₁₀alkyl group, —C(CH₃)₂C(CH₃)₂—,—C(CH₃)₂CH₂C(CH₃)₂—, or —CH₂C(CH₃)₂CH₂—, and Y¹³ and Y¹⁴ areindependently of each other hydrogen, or a C₁-C₁₀alkyl group; Y is agroup of formula

a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1,2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; Ar and Ar′ areindependently of each other

wherein R¹, R^(1′), R² and R^(2′) may be the same or different and areselected from hydrogen or a C₁-C₃₈alkyl group, X⁹² is O, S, CR⁹⁹R^(99′),or NR¹³⁰, X⁹³ is O, S, or NR¹³⁰, X⁹⁴ is O, S, or NR¹³⁰, R⁹⁹, R^(99′),R^(99″) and R^(99*) are independently of each other hydrogen,C₁-C₂₅alkyl, or C₁-C₂₅alkyl substituted with one or more halogen atomsand/or interrupted by one or more oxygen atoms, or two moieties R⁹⁹ andR^(99′) or R^(99″) and R^(99*) can form a 5 or 6 membered alkyl ring,which is optionally substituted with one or more halogen atoms and/orinterrupted by one or more oxygen atoms; R¹²¹, R¹²², R¹²³, R¹²⁴ and R¹²⁵are independently of each other hydrogen, halogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, halogen; orC₁-C₁₈alkoxy; C₁-C₂₅alkyl, which is optionally interrupted by one ormore oxygen or sulphur atoms or is optionally substituted by one or morehalogen atoms, F or C₇-C₂₅arylalkyl; R¹³⁰ is hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, halogen, especially F;or C₁-C₁₈alkoxy; C₁-C₂₅alkyl, which is optionally interrupted by one ormore oxygen or sulphur atoms or is optionally substituted by one or morehalogen atoms; or C₇-C₂₅arylalkyl; and Ar1, Ar1′, Ar2, Ar2′, Ar3 andAr3′ are as defined in claim
 18. 30. The compound according to claim 29of formula